Polymer blends from interpolymers of ethylene/alpha-olefins and flexible molded articles made therefrom

ABSTRACT

Polymer blends comprises 1) at least one ethylene/α-olefin interpolymer and 2) at least one polyolefin, or at least one styrenic block copolymer, or a combination thereof. Such polyolefins include, but are not limited to, high melt strength high density polyethylene and high melt strength polypropylene. The ethylene/α-olefin interpolymers are random block copolymers comprising at least a hard block and at least a soft block. The polyolefins can be homopolymers or interpolymers. The resulting polymer blends can be used to make flexible molded articles.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application No.60/718,245, filed Sep. 16, 2005, which further claims priority to PCTApplication No. PCT/US2005/008917, filed on Mar. 17, 2005, which in turnclaims priority to U.S. Provisional Application No. 60/553,906, filedMar. 17, 2004. For purposes of United States patent practice, thecontents of the provisional application and the PCT application areherein incorporated by reference in their entirety.

FIELD OF THE INVENTION

This invention relates to polymer blends comprising at least oneethylene/α-olefin interpolymer and at least one polyolefin, methods ofmaking the blends, and molded products made from the blends.

BACKGROUND OF THE INVENTION

The manufacture of durable goods in the United States alone accounts formillions of tons of plastics consumption annually. Durable goods aremanufactured products capable of long utility which are found in variousmarkets such as the automotive, construction, medical, food andbeverage, electrical, appliance, business machine, and consumer markets.Some applications in these markets require the uses of flexible polymersor polymer blends. These applications include, but are not limited to,toys, grips, soft touch handles, bumper rub strips, floorings, autofloor mats, wheels, casters, furniture and appliance feet, tags, seals,gaskets such as static and dynamic gaskets, automotive doors, bumperfascia, grill components, rocker panels, hoses, linings, officesupplies, seals, liners, diaphragms, tubes, lids, stoppers, plungertips, delivery systems, kitchen wares, shoes, shoe bladders and shoesoles.

For used in durable goods applications, polymers or polymer blends aredesired to possess good processibility (e.g., moldability), appealingappearance (e.g., clear or colorable), suitable surface properties(e.g., good adhesion to substrates, rubber-like feel, non-stickiness andgood paintability), and a good combination of mechanical properties(e.g., flexibility, heat resistance, abrasion and/or scratch resistance,toughness, tensile strength, and compression set). Some polymers thatpossess suitable properties for durable goods include flexiblepolyvinylchloride (f-PVC), poly(styrene-butadiene-styrene) (SBS),poly(styrene-ethylene/butadiene-styrene) (SEBS), thermoplasticvulcanizates (TPV), thermoplastic poly(urethane) (TPU), and polyolefinssuch as polyolefin homopolymers and polyoelfin interpolymers.

Some polyolefins such as polypropylene (PP) and low density polyethylene(LDPE) have found wide acceptance for use in durable goods applicationsfor their ease of molding, good heat resistance and mechanicalproperties. Furthermore, many formulations based on blends ofpolyolefins and other polymers have been developed to meet the demandsrequired by the production of parts of durable goods. For example, ablend of polypropylene and polyethylene can be used to manufacturefibers for artificial turf applications.

Further, some flexible polymers including some polyolefin homopolymersor polyoelfin interpolymers may be tacky, which is an undesirableproperty in some processes or applications. In general, additives suchas fatty acid amides, waxes or other non-tacky polymers can be mixedwith such flexible polymers to reduce their tackiness. However, suchadditives are only effective to some degree and are known to have someundesirable properties of their own.

Despite the availability of a variety of polyolefins and their blends,there exists a continuing need for new polymers or new polymer blendsthat have improved properties and performance characteristics.

SUMMARY OF THE INVENTION

The aforementioned needs are met by various aspects of the inventions.In one aspect, the invention relates to a polymer blend comprising atleast one ethylene/α-olefin interpolymer and one or more additionalpolymers. The additional polymer can be a polyolefin, styrenic blockcopolymer, polyvinylchloride, thermoplastic polyurethanes, or acombination thereof. In one embodiment, the ethylene/α-olefininterpolymer has a M_(w)/M_(n) from about 1.7 to about 3.5, at least onemelting point, T_(m), in degrees Celsius, and a density, d, ingrams/cubic centimeter, wherein the numerical values of T_(m) and dcorrespond to the relationship:T _(m)≧−2002.9+4538.5(d)−2422.2(d)².

In another embodiment, the ethylene/α-olefin interpolymer has aM_(w)/M_(n) from about 1.7 to about 3.5, and is characterized by a heatof fusion, ΔH in J/g, and a delta quantity, ΔT, in degrees Celsiusdefined as the temperature difference between the tallest DSC peak andthe tallest CRYSTAF peak, wherein the numerical values of ΔT and ΔH havethe following relationships:ΔT>−0.1299(ΔH)+62.81 for ΔH greater than zero and up to 130 J/g,ΔT≧48° C. for ΔH greater than 130 J/g,wherein the CRYSTAF peak is determined using at least 5 percent of thecumulative polymer, and if less than 5 percent of the polymer has anidentifiable CRYSTAF peak, then the CRYSTAF temperature is 30° C.

In another embodiment, the ethylene/α-olefin interpolymer ischaracterized by an elastic recovery, Re, in percent at 300 percentstrain and 1 cycle measured with a compression-molded film of theethylene/α-olefin interpolymer, and has a density, d, in grams/cubiccentimeter, wherein the numerical values of Re and d satisfy thefollowing relationship when the ethylene/α-olefin interpolymer issubstantially free of a cross-linked phase:Re>1481−1629(d).

In another embodiment, the ethylene/α-olefin interpolymer has amolecular fraction which elutes between 40° C. and 130° C. whenfractionated using TREF, characterized in that the fraction has a molarcomonomer content of at least 5 percent higher than that of a comparablerandom ethylene interpolymer fraction eluting between the sametemperatures, wherein said comparable random ethylene interpolymer hasthe same comonomer(s) and has a melt index, density, and molar comonomercontent (based on the whole polymer) within 10 percent of that of theethylene/α-olefin interpolymer.

In another embodiment, the ethylene/α-olefin interpolymer ischaracterized by a storage modulus at 25° C., G′(25° C.), and a storagemodulus at 100° C., G′(100° C.), wherein the ratio of G′(25° C.) toG′(100° C.) is from about 1:1 to about 10:1.

In another embodiment, the ethylene/α-olefin interpolymer has at leastone molecular fraction which elutes between 40° C. and 130° C. whenfractionated using TREF, characterized in that the fraction has a blockindex of at least 0.5 and up to about 1 and a molecular weightdistribution, Mw/Mn, greater than about 1.3. In another embodiment, theethylene/α-olefin interpolymer has an average block index greater thanzero and up to about 1.0 and a molecular weight distribution, Mw/Mn,greater than about 1.3.

In another embodiment, the α-olefin in the ethylene/α-olefininterpolymer is styrene, propylene, 1-butene, 1-hexene, 1-octene,4-methyl-1-pentene, norbornene, 1-decene, 1,5-hexadiene, or acombination thereof.

In another embodiment, the ethylene/α-olefin interpolymer is present inthe range from about 5% to about 95% by weight of the total composition.

In another embodiment, the additional polymer is a polyolefin which isan olefin homopolymer, an olefin copolymer, an olefin terpolymer or acombination thereof. In another embodiment, the additional polymerincludes, but is not limited to, a high melt strength polypropylene, ahigh melt strength high density polyethylene, an ethylene/propylenecopolymer, a styrene-butadiene-styrene block copolymer, anethylene/propylene/diene terpolymer, astyrene-ethylene-co-(butene)-styrene block copolymer or a combinationthereof.

In another embodiment, the polyolefin is a high melt strengthpolypropylene, a high melt strength high density polyethylene, anethylene/propylene copolymer, an ethylene/propylene/diene terpolymer, ora combination thereof. In another embodiment, the polyolefin is apolypropylene having a melt strength of at least 6 cN. In anotherembodiment, the polyolefin is a polypropylene having a melt strength ofat least 10 cN.

In another embodiment, the styrenic block copolymer is astyrene-butadiene-styrene block copolymer, astyrene-ethylene-co-(butene)-styrene block copolymer or a combinationthereof. In another embodiment, the styrenic block copolymer is astyrene-butadiene-styrene block copolymer. In another embodiment, thestyrenic block copolymer is a styrene-ethylene/butylene-styrene blockcopolymer.

In another embodiment, the polymer blend further comprises at least anadditive, which in some instances may be a slip agent, anti-blockingagent, plasticizer, oil, antioxidant, UV stabilizer, colorant orpigment, filler, lubricant, antifogging agent, flow aid, coupling agent,cross-linking agent, nucleating agent, surfactant, solvent, flameretardant, antistatic agent or a combination thereof

In another aspect, the invention relates to flexible molded articlecomprising the polymer blend disclosed herein. In some embodiments, theflexible molded article includes toys, grips, soft touch handles, bumperrub strips, floorings, auto floor mats, wheels, casters, furniture andappliance feet, tags, seals, gaskets such as static and dynamic gaskets,automotive doors, bumper fascia, grill components, rocker panels, hoses,linings, office supplies, seals, liners, diaphragms, tubes, lids,stoppers, plunger tips, delivery systems, kitchen wares, shoes, shoebladders, shoe soles and combinations thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the melting point/density relationship for the inventivepolymers (represented by diamonds) as compared to traditional randomcopolymers (represented by circles) and Ziegler-Natta copolymers(represented by triangles).

FIG. 2 shows plots of delta DSC-CRYSTAF as a function of DSC MeltEnthalpy for various polymers. The diamonds represent randomethylene/octene copolymers; the squares represent polymer examples 1-4;the triangles represent polymer examples 5-9; and the circles representpolymer Examples 10-19. The “X” symbols represent polymer ComparativeExamples A*-F*.

FIG. 3 shows the effect of density on elastic recovery for unorientedfilms made from inventive interpolymers (represented by the squares andcircles) and traditional copolymers (represented by the triangles whichare various Dow AFFINITY® polymers). The squares represent inventiveethylene/butene copolymers; and the circles represent inventiveethylene/octene copolymers.

FIG. 4 is a plot of octene content of TREF fractionatedethylene/1-octene copolymer fractions versus TREF elution temperature ofthe fraction for the polymer of Example 5 (represented by the circles)and comparative polymer Comparative Examples E* and F* (represented bythe “X” symbols). The diamonds represent traditional randomethylene/octene copolymers.

FIG. 5 is a plot of octene content of TREF fractionatedethylene/1-octene copolymer fractions versus TREF elution temperature ofthe fraction for the polymer of Example 5 (curve 1) and for polymerComparative Examples F* (curve 2). The squares represent polymerComparative Examples F*; and the triangles represent Example 5.

FIG. 6 is a graph of the log of storage modulus as a function oftemperature for comparative ethylene/1-octene copolymer (curve 2) andpropylene/ethylene copolymer (curve 3) and for two ethylene/1-octeneblock copolymers of the invention made with differing quantities ofchain shuttling agent (curves 1).

FIG. 7 shows a plot of TMA (1 mm) versus flex modulus for some inventivepolymers (represented by the diamonds), as compared to some knownpolymers. The triangles represent various Dow VERSIFY® polymers; thecircles represent various random ethylene/styrene copolymers; and thesquares represent various Dow AFFINITY® polymers.

FIG. 8 shows tensile recovery of two-component blends containingComponent A (i.e., KRATON® G1652, a SEBS) and Component B (i.e., DowAFFINITY® EG8100 or inventive Polymer 19a, 19b or 19i). The cyclesrepresent blends containing KRATON® G1652 and Dow AFFINITY® EG8100(i.e., Comparative Examples Y1-Y5 having respectively 0%, 25%, 50%, 75%and 100% of Dow AFFINITY® EG8100). The diamonds represent blendscontaining KRATON® G1652 and inventive Polymer 19a (i.e., Examples 34-37having respectively 25%, 50%, 75% and 100% of Polymer 19a). Thetriangles represent the blends containing KRATON® G1652 and inventivePolymer 19b (i.e., Examples 38-41 having respectively 25%, 50%, 75% and100% of Polymer 19b). The squares represent blends containing KRATON®G1652 and inventive Polymer 19i (i.e., Examples 42-45 havingrespectively 25%, 50%, 75% and 100% of Polymer 19i).

FIG. 9 shows heat resistance properties (i.e., TMA temperatures) oftwo-component blends containing Component A (i.e., KRATON® G1652, aSEBS) and Component B (i.e., Dow AFFINITY® EG8100 or inventive Polymer19a, 19b or 19i). The cycles represent blends containing KRATON® G1652and Dow AFFINITY® EG8100 (i.e., Comparative Examples Y1-Y5 havingrespectively 0%, 25%, 50%, 75% and 100% of Dow AFFINITY®EG8100). Thediamonds represent blends containing KRATON® G1652 and inventive Polymer19a (i.e., Examples 34-37 having respectively 25%, 50%, 75% and 100% ofPolymer 19a). The triangles represent the blends containing KRATON®G1652 and inventive Polymer 19b (i.e., Examples 38-41 havingrespectively 25%, 50%, 75% and 100% of Polymer 19b). The squaresrepresent blends containing KRATON® G1652 and inventive Polymer 19i(i.e., Examples 42-45 having respectively 25%, 50%, 75% and 100% ofPolymer 19i).

DETAILED DESCRIPTION OF THE INVENTION

General Definitions

“Polymer” means a polymeric compound prepared by polymerizing monomers,whether of the same or a different type. The generic term “polymer”embraces the terms “homopolymer,” “copolymer,” “terpolymer” as well as“interpolymer.”

“Interpolymer” means a polymer prepared by the polymerization of atleast two different types of monomers. The generic term “interpolymer”includes the term “copolymer” (which is usually employed to refer to apolymer prepared from two different monomers) as well as the term“terpolymer” (which is usually employed to refer to a polymer preparedfrom three different types of monomers). It also encompasses polymersmade by polymerizing four or more types of monomers.

The term “ethylene/α-olefin interpolymer” generally refers to polymerscomprising ethylene and an α-olefin having 3 or more carbon atoms.Preferably, ethylene comprises the majority mole fraction of the wholepolymer, i.e., ethylene comprises at least about 50 mole percent of thewhole polymer. More preferably ethylene comprises at least about 60 molepercent, at least about 70 mole percent, or at least about 80 molepercent, with the substantial remainder of the whole polymer comprisingat least one other comonomer that is preferably an α-olefin having 3 ormore carbon atoms. For many ethylene/octene copolymers, the preferredcomposition comprises an ethylene content greater than about 80 molepercent of the whole polymer and an octene content of from about 10 toabout 15, preferably from about 15 to about 20 mole percent of the wholepolymer. In some embodiments, the ethylene/α-olefin interpolymers do notinclude those produced in low yields or in a minor amount or as aby-product of a chemical process. While the ethylene/α-olefininterpolymers can be blended with one or more polymers, the as-producedethylene/α-olefin interpolymers are substantially pure and oftencomprise a major component of the reaction product of a polymerizationprocess.

The ethylene/α-olefin interpolymers comprise ethylene and one or morecopolymerizable α-olefin comonomers in polymerized form, characterizedby multiple blocks or segments of two or more polymerized monomer unitsdiffering in chemical or physical properties. That is, theethylene/α-olefin interpolymers are block interpolymers, preferablymulti-block interpolymers or copolymers. The terms “interpolymer” andcopolymer” are used interchangeably herein. In some embodiments, themulti-block copolymer can be represented by the following formula:(AB)_(n)where n is at least 1, preferably an integer greater than 1, such as 2,3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or higher, “A”represents a hard block or segment and “B” represents a soft block orsegment. Preferably, As and Bs are linked in a substantially linearfashion, as opposed to a substantially branched or substantiallystar-shaped fashion. In other embodiments, A blocks and B blocks arerandomly distributed along the polymer chain. In other words, the blockcopolymers usually do not have a structure as follows.AAA-AA-BBB—BBIn still other embodiments, the block copolymers do not usually have athird type of block, which comprises different comonomer(s). In yetother embodiments, each of block A and block B has monomers orcomonomers substantially randomly distributed within the block. In otherwords, neither block A nor block B comprises two or more sub-segments(or sub-blocks) of distinct composition, such as a tip segment, whichhas a substantially different composition than the rest of the block.

The multi-block polymers typically comprise various amounts of “hard”and “soft” segments. “Hard” segments refer to blocks of polymerizedunits in which ethylene is present in an amount greater than about 95weight percent, and preferably greater than about 98 weight percentbased on the weight of the polymer. In other words, the comonomercontent (content of monomers other than ethylene) in the hard segmentsis less than about 5 weight percent, and preferably less than about 2weight percent based on the weight of the polymer. In some embodiments,the hard segments comprises all or substantially all ethylene. “Soft”segments, on the other hand, refer to blocks of polymerized units inwhich the comonomer content (content of monomers other than ethylene) isgreater than about 5 weight percent, preferably greater than about 8weight percent, greater than about 10 weight percent, or greater thanabout 15 weight percent based on the weight of the polymer. In someembodiments, the comonomer content in the soft segments can be greaterthan about 20 weight percent, greater than about 25 weight percent,greater than about 30 weight percent, greater than about 35 weightpercent, greater than about 40 weight percent, greater than about 45weight percent, greater than about 50 weight percent, or greater thanabout 60 weight percent.

The soft segments can often be present in a block interpolymer fromabout 1 weight percent to about 99 weight percent of the total weight ofthe block interpolymer, preferably from about 5 weight percent to about95 weight percent, from about 10 weight percent to about 90 weightpercent, from about 15 weight percent to about 85 weight percent, fromabout 20 weight percent to about 80 weight percent, from about 25 weightpercent to about 75 weight percent, from about 30 weight percent toabout 70 weight percent, from about 35 weight percent to about 65 weightpercent, from about 40 weight percent to about 60 weight percent, orfrom about 45 weight percent to about 55 weight percent of the totalweight of the block interpolymer. Conversely, the hard segments can bepresent in similar ranges. The soft segment weight percentage and thehard segment weight percentage can be calculated based on data obtainedfrom DSC or NMR. Such methods and calculations are disclosed in aconcurrently filed U.S. patent application Ser. No. ______ (insert whenknown), Attorney Docket No. 385063-999558, entitled “Ethylene/α-OlefinBlock Interpolymers”, filed on Mar. 15, 2006, in the name of Colin L. P.Shan, Lonnie Hazlitt, et. al. and assigned to Dow Global TechnologiesInc., the disclose of which is incorporated by reference herein in itsentirety.

The term “crystalline” if employed, refers to a polymer that possesses afirst order transition or crystalline melting point (Tm) as determinedby differential scanning calorimetry (DSC) or equivalent technique. Theterm may be used interchangeably with the term “semicrystalline”. Theterm “amorphous” refers to a polymer lacking a crystalline melting pointas determined by differential scanning calorimetry (DSC) or equivalenttechnique.

The term “multi-block copolymer” or “segmented copolymer” refers to apolymer comprising two or more chemically distinct regions or segments(referred to as “blocks”) preferably joined in a linear manner, that is,a polymer comprising chemically differentiated units which are joinedend-to-end with respect to polymerized ethylenic functionality, ratherthan in pendent or grafted fashion. In a preferred embodiment, theblocks differ in the amount or type of comonomer incorporated therein,the density, the amount of crystallinity, the crystallite sizeattributable to a polymer of such composition, the type or degree oftacticity (isotactic or syndiotactic), regio-regularity orregio-irregularity, the amount of branching, including long chainbranching or hyper-branching, the homogeneity, or any other chemical orphysical property. The multi-block copolymers are characterized byunique distributions of both polydispersity index (PDI or Mw/Mn), blocklength distribution, and/or block number distribution due to the uniqueprocess making of the copolymers. More specifically, when produced in acontinuous process, the polymers desirably possess PDI from 1.7 to 2.9,preferably from 1.8 to 2.5, more preferably from 1.8 to 2.2, and mostpreferably from 1.8 to 2.1. When produced in a batch or semi-batchprocess, the polymers possess PDI from 1.0 to 2.9, preferably from 1.3to 2.5, more preferably from 1.4 to 2.0, and most preferably from 1.4 to1.8.

In the following description, all numbers disclosed herein areapproximate values, regardless whether the word “about” or “approximate”is used in connection therewith. They may vary by 1 percent, 2 percent,5 percent, or, sometimes, 10 to 20 percent. Whenever a numerical rangewith a lower limit, R^(L) and an upper limit, R^(U), is disclosed, anynumber falling within the range is specifically disclosed. Inparticular, the following numbers within the range are specificallydisclosed: R═R^(L)+k*(R^(U)−R^(L)), wherein k is a variable ranging from1 percent to 100 percent with a 1 percent increment, i.e., k is 1percent, 2 percent, 3 percent, 4 percent, 5 percent, . . . , 50 percent,51 percent, 52 percent, . . . , 95 percent, 96 percent, 97 percent, 98percent, 99 percent, or 100 percent. Moreover, any numerical rangedefined by two R numbers as defined in the above is also specificallydisclosed.

Embodiments of the invention provide polymer blends comprising at leastone ethylene/α-olefin block interpolymer (to be described below) and oneor more polymers, which are different than the ethylene/α-olefin blockinterpolymer. The additional polymers include, but are not limited to,thermoplastic polymers, elastomers, and rubbers, such as polyolefins,styrenic block copolymers, etc. The term “different” when referring totwo polymers means that the two polymers differ in composition(comonomer type, comonomer content, etc.), structure, property, or acombination of both. For example, a block ethylene/octene copolymer isdifferent than a random ethylene/octene copolymer, even if they have thesame amount of comonomers. A block ethylene/octene copolymer isdifferent than an ethylene/butane copolymer, regardless of whether it isa random or block copolymer or whether it has the same comonomercontent. Two polyolefins also are considered different if they have adifferent molecular weight, even though they have the same structure andcomposition. Moreover, a random homogeneous ethylene/octene copolymer isdifferent than a random heterogenous ethylene/octene copolymer, even ifall other parameters may be the same.

The polymer blends possess unique physical and mechanical propertiesthat are suitable for making molded articles for a variety ofapplications. The blends have relatively low modulus, while maintainingrelatively high heat resistance. Such balance of properties makes theblends suitable for making flexible molded articles. The molded articlesshould have an upper use or service temperature of at least 40° C., atleast 50° C., at least 60° C., at least 80° C., or at least 90° C. Theflexural modulus of the blends should be less than 20,000 psi, less than10,000 psi, less than 5000 psi, less than 1000 psi, less than 500 psi.

Ethylene/α-Olefin Interpolymers

The ethylene/α-olefin interpolymers used in embodiments of the invention(also referred to as “inventive interpolymer” or “inventive polymer”)comprise ethylene and one or more copolymerizable α-olefin comonomers inpolymerized form, characterized by multiple blocks or segments of two ormore polymerized monomer units differing in chemical or physicalproperties (block interpolymer), preferably a multi-block copolymer. Theethylene/α-olefin interpolymers are characterized by one or more of theaspects described as follows.

In one aspect, the ethylene/α-olefin interpolymers used in embodimentsof the invention have a M_(w)/M_(n) from about 1.7 to about 3.5 and atleast one melting point, T_(m), in degrees Celsius and density, d, ingrams/cubic centimeter, wherein the numerical values of the variablescorrespond to the relationship:T _(m)>−2002.9+4538.5(d)−2422.2(d)², and preferablyT _(m)≧−6288.1+13141(d)−6720.3(d)₂, and more preferablyT _(m)≧858.91−1825.3(d)+1112.8(d)².

Such melting point/density relationship is illustrated in FIG. 1. Unlikethe traditional random copolymers of ethylene/α-olefins whose meltingpoints decrease with decreasing densities, the inventive interpolymers(represented by diamonds) exhibit melting points substantiallyindependent of the density, particularly when density is between about0.87 g/cc to about 0.95 g/cc. For example, the melting point of suchpolymers are in the range of about 110° C. to about 130° C. when densityranges from 0.875 g/cc to about 0.945 g/cc. In some embodiments, themelting point of such polymers are in the range of about 115° C. toabout 125° C. when density ranges from 0.875 g/cc to about 0.945 g/cc.

In another aspect, the ethylene/α-olefin interpolymers comprise, inpolymerized form, ethylene and one or more α-olefins and arecharacterized by a ΔT, in degree Celsius, defined as the temperature forthe tallest Differential Scanning Calorimetry (“DSC”) peak minus thetemperature for the tallest Crystallization Analysis Fractionation(“CRYSTAF”) peak and a heat of fusion in J/g, ΔH, and ΔT and ΔH satisfythe following relationships:ΔT>−0.1299(ΔH)+62.81, and preferablyΔT≧−0.1299(ΔH)+64.38, and more preferablyΔT≧−0.1299(ΔH)+65.95,for ΔH up to 130 J/g. Moreover, ΔT is equal to or greater than 48° C.for ΔH greater than 130 J/g. The CRYSTAF peak is determined using atleast 5 percent of the cumulative polymer (that is, the peak mustrepresent at least 5 percent of the cumulative polymer), and if lessthan 5 percent of the polymer has an identifiable CRYSTAF peak, then theCRYSTAF temperature is 30° C., and ΔH is the numerical value of the heatof fusion in J/g. More preferably, the highest CRYSTAF peak contains atleast 10 percent of the cumulative polymer. FIG. 2 shows plotted datafor inventive polymers as well as comparative examples. Integrated peakareas and peak temperatures are calculated by the computerized drawingprogram supplied by the instrument maker. The diagonal line shown forthe random ethylene octene comparative polymers corresponds to theequation ΔT=−0.1299(ΔH)+62.81.

In yet another aspect, the ethylene/α-olefin interpolymers have amolecular fraction which elutes between 40° C. and 130° C. whenfractionated using Temperature Rising Elution Fractionation (“TREF”),characterized in that said fraction has a molar comonomer contenthigher, preferably at least 5 percent higher, more preferably at least10 percent higher, than that of a comparable random ethyleneinterpolymer fraction eluting between the same temperatures, wherein thecomparable random ethylene interpolymer contains the same comonomer(s),and has a melt index, density, and molar comonomer content (based on thewhole polymer) within 10 percent of that of the block interpolymer.Preferably, the Mw/Mn of the comparable interpolymer is also within 10percent of that of the block interpolymer and/or the comparableinterpolymer has a total comonomer content within 10 weight percent ofthat of the block interpolymer.

In still another aspect, the ethylene/α-olefin interpolymers arecharacterized by an elastic recovery, Re, in percent at 300 percentstrain and 1 cycle measured on a compression-molded film of anethylene/α-olefin interpolymer, and has a density, d, in grams/cubiccentimeter, wherein the numerical values of Re and d satisfy thefollowing relationship when ethylene/α-olefin interpolymer issubstantially free of a cross-linked phase:Re>1481−1629(d); and preferablyRe≧1491−1629(d); and more preferablyRe≧1501−1629(d); and even more preferablyRe≧1511−1629(d).

FIG. 3 shows the effect of density on elastic recovery for unorientedfilms made from certain inventive interpolymers and traditional randomcopolymers. For the same density, the inventive interpolymers havesubstantially higher elastic recoveries.

In some embodiments, the ethylene/α-olefin interpolymers have a tensilestrength above 10 MPa, preferably a tensile strength ≧11 MPa, morepreferably a tensile strength ≧13 MPa and/or an elongation at break ofat least 600 percent, more preferably at least 700 percent, highlypreferably at least 800 percent, and most highly preferably at least 900percent at a crosshead separation rate of 11 cm/minute.

In other embodiments, the ethylene/α-olefin interpolymers have (1) astorage modulus ratio, G′(25° C.)/G′(100° C.), of from 1 to 50,preferably from 1 to 20, more preferably from 1 to 10; and/or (2) a 70°C. compression set of less than 80 percent, preferably less than 70percent, especially less than 60 percent, less than 50 percent, or lessthan 40 percent, down to a compression set of 0 percent.

In still other embodiments, the ethylene/α-olefin interpolymers have a70° C. compression set of less than 80 percent, less than 70 percent,less than 60 percent, or less than 50 percent. Preferably, the 70° C.compression set of the interpolymers is less than 40 percent, less than30 percent, less than 20 percent, and may go down to about 0 percent.

In some embodiments, the ethylene/α-olefin interpolymers have a heat offusion of less than 85 J/g and/or a pellet blocking strength of equal toor less than 100 pounds/foot² (4800 Pa), preferably equal to or lessthan 50 lbs/ft² (2400 Pa), especially equal to or less than 5 lbs/ft²(240 Pa), and as low as 0 lbs/ft² (0 Pa).

In other embodiments, the ethylene/α-olefin interpolymers comprise, inpolymerized form, at least 50 mole percent ethylene and have a 70° C.compression set of less than 80 percent, preferably less than 70 percentor less than 60 percent, most preferably less than 40 to 50 percent anddown to close zero percent.

In some embodiments, the multi-block copolymers possess a PDI fitting aSchultz-Flory distribution rather than a Poisson distribution. Thecopolymers are further characterized as having both a polydisperse blockdistribution and a polydisperse distribution of block sizes andpossessing a most probable distribution of block lengths. Preferredmulti-block copolymers are those containing 4 or more blocks or segmentsincluding terminal blocks. More preferably, the copolymers include atleast 5, 10 or 20 blocks or segments including terminal blocks.

Comonomer content may be measured using any suitable technique, withtechniques based on nuclear magnetic resonance (“NMR”) spectroscopypreferred. Moreover, for polymers or blends of polymers havingrelatively broad TREF curves, the polymer desirably is firstfractionated using TREF into fractions each having an eluted temperaturerange of 10° C. or less. That is, each eluted fraction has a collectiontemperature window of 10° C. or less. Using this technique, said blockinterpolymers have at least one such fraction having a higher molarcomonomer content than a corresponding fraction of the comparableinterpolymer.

In another aspect, the inventive polymer is an olefin interpolymer,preferably comprising ethylene and one or more copolymerizablecomonomers in polymerized form, characterized by multiple blocks (i.e.,at least two blocks) or segments of two or more polymerized monomerunits differing in chemical or physical properties (blockedinterpolymer), most preferably a multi-block copolymer, said blockinterpolymer having a peak (but not just a molecular fraction) whichelutes between 40° C. and 130° C. (but without collecting and/orisolating individual fractions), characterized in that said peak, has acomonomer content estimated by infra-red spectroscopy when expandedusing a full width/half maximum (FWHM) area calculation, has an averagemolar comonomer content higher, preferably at least 5 percent higher,more preferably at least 10 percent higher, than that of a comparablerandom ethylene interpolymer peak at the same elution temperature andexpanded using a full width/half maximum (FWHM) area calculation,wherein said comparable random ethylene interpolymer has the samecomonomer(s) and has a melt index, density, and molar comonomer content(based on the whole polymer) within 10 percent of that of the blockedinterpolymer. Preferably, the Mw/Mn of the comparable interpolymer isalso within 10 percent of that of the blocked interpolymer and/or thecomparable interpolymer has a total comonomer content within 10 weightpercent of that of the blocked interpolymer. The full width/half maximum(FWHM) calculation is based on the ratio of methyl to methylene responsearea [CH₃/CH₂] from the ATREF infra-red detector, wherein the tallest(highest) peak is identified from the base line, and then the FWHM areais determined. For a distribution measured using an ATREF peak, the FWHMarea is defined as the area under the curve between T₁ and T₂, where T₁and T₂ are points determined, to the left and right of the ATREF peak,by dividing the peak height by two, and then drawing a line horizontalto the base line, that intersects the left and right portions of theATREF curve. A calibration curve for comonomer content is made usingrandom ethylene/α-olefin copolymers, plotting comonomer content from NMRversus FWHM area ratio of the TREF peak. For this infra-red method, thecalibration curve is generated for the same comonomer type of interest.The comonomer content of TREF peak of the inventive polymer can bedetermined by referencing this calibration curve using its FWHMmethyl:methylene area ratio [CH₃/CH₂] of the TREF peak.

Comonomer content may be measured using any suitable technique, withtechniques based on nuclear magnetic resonance (NMR) spectroscopypreferred. Using this technique, said blocked interpolymers has highermolar comonomer content than a corresponding comparable interpolymer.

Preferably, for interpolymers of ethylene and 1-octene, the blockinterpolymer has a comonomer content of the TREF fraction elutingbetween 40 and 130° C. greater than or equal to the quantity(−0.2013)T+20.07, more preferably greater than or equal to the quantity(−0.2013) T+21.07, where T is the numerical value of the peak elutiontemperature of the TREF fraction being compared, measured in ° C.

FIG. 4 graphically depicts an embodiment of the block interpolymers ofethylene and 1-octene where a plot of the comonomer content versus TREFelution temperature for several comparable ethylene/1-octeneinterpolymers (random copolymers) are fit to a line representing(−0.2013)T+20.07 (solid line). The line for the equation(−0.2013)T+21.07 is depicted by a dotted line. Also depicted are thecomonomer contents for fractions of several block ethylene/1-octeneinterpolymers of the invention (multi-block copolymers). All of theblock interpolymer fractions have significantly higher 1-octene contentthan either line at equivalent elution temperatures. This result ischaracteristic of the inventive interpolymer and is believed to be dueto the presence of differentiated blocks within the polymer chains,having both crystalline and amorphous nature.

FIG. 5 graphically displays the TREF curve and comonomer contents ofpolymer fractions for Example 5 and comparative F to be discussed below.The peak eluting from 40 to 130° C., preferably from 60° C. to 95° C.for both polymers is fractionated into three parts, each part elutingover a temperature range of less than 10° C. Actual data for Example 5is represented by triangles. The skilled artisan can appreciate that anappropriate calibration curve may be constructed for interpolymerscontaining different comonomers and a line used as a comparison fittedto the TREF values obtained from comparative interpolymers of the samemonomers, preferably random copolymers made using a metallocene or otherhomogeneous catalyst composition. Inventive interpolymers arecharacterized by a molar comonomer content greater than the valuedetermined from the calibration curve at the same TREF elutiontemperature, preferably at least 5 percent greater, more preferably atleast 10 percent greater.

In addition to the above aspects and properties described herein, theinventive polymers can be characterized by one or more additionalcharacteristics. In one aspect, the inventive polymer is an olefininterpolymer, preferably comprising ethylene and one or morecopolymerizable comonomers in polymerized form, characterized bymultiple blocks or segments of two or more polymerized monomer unitsdiffering in chemical or physical properties (blocked interpolymer),most preferably a multi-block copolymer, said block interpolymer havinga molecular fraction which elutes between 40° C. and 130° C., whenfractionated using TREF increments, characterized in that said fractionhas a molar comonomer content higher, preferably at least 5 percenthigher, more preferably at least 10, 15, 20 or 25 percent higher, thanthat of a comparable random ethylene interpolymer fraction elutingbetween the same temperatures, wherein said comparable random ethyleneinterpolymer comprises the same comonomer(s), preferably it is the samecomonomer(s), and a melt index, density, and molar comonomer content(based on the whole polymer) within 10 percent of that of the blockedinterpolymer. Preferably, the Mw/Mn of the comparable interpolymer isalso within 10 percent of that of the blocked interpolymer and/or thecomparable interpolymer has a total comonomer content within 10 weightpercent of that of the blocked interpolymer.

Preferably, the above interpolymers are interpolymers of ethylene and atleast one α-olefin, especially those interpolymers having a wholepolymer density from about 0.855 to about 0.935 g/cm³, and moreespecially for polymers having more than about 1 mole percent comonomer,the blocked interpolymer has a comonomer content of the TREF fractioneluting between 40 and 130° C. greater than or equal to the quantity(−0.1356) T+13.89, more preferably greater than or equal to the quantity(−0.1356) T+14.93, and most preferably greater than or equal to thequantity (−0.2013)T+21.07, where T is the numerical value of the peakATREF elution temperature of the TREF fraction being compared, measuredin ° C.

Preferably, for the above interpolymers of ethylene and at least onealpha-olefin especially those interpolymers having a whole polymerdensity from about 0.855 to about 0.935 g/cm³, and more especially forpolymers having more than about 1 mole percent comonomer, the blockedinterpolymer has a comonomer content of the TREF fraction elutingbetween 40 and 130° C. greater than or equal to the quantity (−0.2013)T+20.07, more preferably greater than or equal to the quantity (−0.2013)T+21.07, where T is the numerical value of the peak elution temperatureof the TREF fraction being compared, measured in ° C.

In still another aspect, the inventive polymer is an olefininterpolymer, preferably comprising ethylene and one or morecopolymerizable comonomers in polymerized form, characterized bymultiple blocks or segments of two or more polymerized monomer unitsdiffering in chemical or physical properties (blocked interpolymer),most preferably a multi-block copolymer, said block interpolymer havinga molecular fraction which elutes between 40° C. and 130° C., whenfractionated using TREF increments, characterized in that every fractionhaving a comonomer content of at least about 6 mole percent, has amelting point greater than about 100° C. For those fractions having acomonomer content from about 3 mole percent to about 6 mole percent,every fraction has a DSC melting point of about 110° C. or higher. Morepreferably, said polymer fractions, having at least 1 mol percentcomonomer, has a DSC melting point that corresponds to the equation:T _(m)≧(−5.5926)(mol percent comonomer in the fraction)+135.90.

In yet another aspect, the inventive polymer is an olefin interpolymer,preferably comprising ethylene and one or more copolymerizablecomonomers in polymerized form, characterized by multiple blocks orsegments of two or more polymerized monomer units differing in chemicalor physical properties (blocked interpolymer), most preferably amulti-block copolymer, said block interpolymer having a molecularfraction which elutes between 40° C. and 130° C., when fractionatedusing TREF increments, characterized in that every fraction that has anATREF elution temperature greater than or equal to about 76° C., has amelt enthalpy (heat of fusion) as measured by DSC, corresponding to theequation:Heat of fusion (J/gm)≦(3.1718)(ATREF elution temperature inCelsius)−136.58,

The inventive block interpolymers have a molecular fraction which elutesbetween 40° C. and 130° C., when fractionated using TREF increments,characterized in that every fraction that has an ATREF elutiontemperature between 40° C. and less than about 76° C., has a meltenthalpy (heat of fusion) as measured by DSC, corresponding to theequation:Heat of fusion (J/gm)≦(1.1312)(ATREF elution temperature inCelsius)+22.97.ATREF Peak Comonomer Composition Measurement by Infra-Red Detector

The comonomer composition of the TREF peak can be measured using an IR4infra-red detector available from Polymer Char, Valencia, Spain(http://www.polymerchar.com/).

The “composition mode” of the detector is equipped with a measurementsensor (CH₂) and composition sensor (CH₃) that are fixed narrow bandinfra-red filters in the region of 2800-3000 cm⁻¹. The measurementsensor detects the methylene (CH₂) carbons on the polymer (whichdirectly relates to the polymer concentration in solution) while thecomposition sensor detects the methyl (CH₃) groups of the polymer. Themathematical ratio of the composition signal (CH₃) divided by themeasurement signal (CH₂) is sensitive to the comonomer content of themeasured polymer in solution and its response is calibrated with knownethylene alpha-olefin copolymer standards.

The detector when used with an ATREF instrument provides both aconcentration (CH₂) and composition (CH₃) signal response of the elutedpolymer during the TREF process. A polymer specific calibration can becreated by measuring the area ratio of the CH₃ to CH₂ for polymers withknown comonomer content (preferably measured by NMR). The comonomercontent of an ATREF peak of a polymer can be estimated by applying a thereference calibration of the ratio of the areas for the individual CH₃and CH₂ response (i.e. area ratio CH₃/CH₂ versus comonomer content).

The area of the peaks can be calculated using a full width/half maximum(FWHM) calculation after applying the appropriate baselines to integratethe individual signal responses from the TREF chromatogram. The fullwidth/half maximum calculation is based on the ratio of methyl tomethylene response area [CH₃/CH₂] from the ATREF infra-red detector,wherein the tallest (highest) peak is identified from the base line, andthen the FWHM area is determined. For a distribution measured using anATREF peak, the FWHM area is defined as the area under the curve betweenT1 and T2, where T1 and T2 are points determined, to the left and rightof the ATREF peak, by dividing the peak height by two, and then drawinga line horizontal to the base line, that intersects the left and rightportions of the ATREF curve.

The application of infra-red spectroscopy to measure the comonomercontent of polymers in this ATREF-infra-red method is, in principle,similar to that of GPC/FTIR systems as described in the followingreferences: Markovich, Ronald P.; Hazlitt, Lonnie G.; Smith, Linley;“Development of gel-permeation chromatography-Fourier transform infraredspectroscopy for characterization of ethylene-based polyolefincopolymers”. Polymeric Materials Science and Engineering (1991), 65,98-100.; and Deslauriers, P. J.; Rohlfing, D. C.; Shieh, E. T.;“Quantifying short chain branching microstructures in ethylene-1-olefincopolymers using size exclusion chromatography and Fourier transforminfrared spectroscopy (SEC-FTIR)”, Polymer (2002), 43, 59-170., both ofwhich are incorporated by reference herein in their entirety.

In other embodiments, the inventive ethylene/α-olefin interpolymer ischaracterized by an average block index, ABI, which is greater than zeroand up to about 1.0 and a molecular weight distribution, M_(w)/M_(n),greater than about 1.3. The average block index, ABI, is the weightaverage of the block index (“BI”) for each of the polymer fractionsobtained in preparative TREF from 20° C. and 110° C., with an incrementof 5° C.:ABI=Σ(w _(i) BI _(i))

where BI_(i) is the block index for the ith fraction of the inventiveethylene/α-olefin interpolymer obtained in preparative TREF, and w_(i)is the weight percentage of the ith fraction.

For each polymer fraction, BI is defined by one of the two followingequations (both of which give the same BI value): $\begin{matrix}{{BI} = \frac{{1/T_{X}} - {1/T_{XO}}}{{1/T_{A}} - {1/T_{AB}}}} & {or} & {{BI} = {- \frac{{{Ln}\quad P_{X}} - {{Ln}\quad P_{XO}}}{{{Ln}\quad P_{A}} - {{Ln}\quad P_{AB}}}}}\end{matrix}$

where T_(X) is the preparative ATREF elution temperature for the ithfraction (preferably expressed in Kelvin), P_(X) is the ethylene molefraction for the ith fraction, which can be measured by NMR or IR asdescribed above. P_(AB) is the ethylene mole fraction of the wholeethylene/α-olefin interpolymer (before fractionation), which also can bemeasured by NMR or IR. T_(A) and P_(A) are the ATREF elution temperatureand the ethylene mole fraction for pure “hard segments” (which refer tothe crystalline segments of the interpolymer). As a first orderapproximation, the T_(A) and P_(A) values are set to those for highdensity polyethylene homopolymer, if the actual values for the “hardsegments” are not available. For calculations performed herein, T_(A) is372° K, P_(A) is 1.

T_(AB) is the ATREF temperature for a random copolymer of the samecomposition and having an ethylene mole fraction of P_(AB). T_(AB) canbe calculated from the following equation:LnP _(AB) =α/T _(AB)+β

where α and β are two constants which can be determined by calibrationusing a number of known random ethylene copolymers. It should be notedthat α and β may vary from instrument to instrument. Moreover, one wouldneed to create their own calibration curve with the polymer compositionof interest and also in a similar molecular weight range as thefractions. There is a slight molecular weight effect. If the calibrationcurve is obtained from similar molecular weight ranges, such effectwould be essentially negligible. In some embodiments, random ethylenecopolymers satisfy the following relationship:LnP=−237.83/T _(ATREF)+0.639

T_(XO) is the ATREF temperature for a random copolymer of the samecomposition and having an ethylene mole fraction of P_(X). T_(XO) can becalculated from LnP_(X)=α/T_(XO)+β Conversely, P_(XO) is the ethylenemole fraction for a random copolymer of the same composition and havingan ATREF temperature of T_(X), which can be calculated fromLnP_(XO)=α/T_(X)+β.

Once the block index (BI) for each preparative TREF fraction isobtained, the weight average block index, ABI, for the whole polymer canbe calculated. In some embodiments, ABI is greater than zero but lessthan about 0.3 or from about 0.1 to about 0.3. In other embodiments, ABIis greater than about 0.3 and up to about 1.0. Preferably, ABI should bein the range of from about 0.4 to about 0.7, from about 0.5 to about0.7, or from about 0.6 to about 0.9. In some embodiments, ABI is in therange of from about 0.3 to about 0.9, from about 0.3 to about 0.8, orfrom about 0.3 to about 0.7, from about 0.3 to about 0.6, from about 0.3to about 0.5, or from about 0.3 to about 0.4. In other embodiments, ABIis in the range of from about 0.4 to about 1.0, from about 0.5 to about1.0, or from about 0.6 to about 1.0, from about 0.7 to about 1.0, fromabout 0.8 to about 1.0, or from about 0.9 to about 1.0.

Another characteristic of the inventive ethylene/α-olefin interpolymeris that the inventive ethylene/α-olefin interpolymer comprises at leastone polymer fraction which can be obtained by preparative TREF, whereinthe fraction has a block index greater than about 0.1 and up to about1.0 and a molecular weight distribution, M_(w)/M_(n), greater than about1.3. In some embodiments, the polymer fraction has a block index greaterthan about 0.6 and up to about 1.0, greater than about 0.7 and up toabout 1.0, greater than about 0.8 and up to about 1.0, or greater thanabout 0.9 and up to about 1.0. In other embodiments, the polymerfraction has a block index greater than about 0.1 and up to about 1.0,greater than about 0.2 and up to about 1.0, greater than about 0.3 andup to about 1.0, greater than about 0.4 and up to about 1.0, or greaterthan about 0.4 and up to about 1.0. In still other embodiments, thepolymer fraction has a block index greater than about 0.1 and up toabout 0.5, greater than about 0.2 and up to about 0.5, greater thanabout 0.3 and up to about 0.5, or greater than about 0.4 and up to about0.5. In yet other embodiments, the polymer fraction has a block indexgreater than about 0.2 and up to about 0.9, greater than about 0.3 andup to about 0.8, greater than about 0.4 and up to about 0.7, or greaterthan about 0.5 and up to about 0.6.

For copolymers of ethylene and an α-olefin, the inventive polymerspreferably possess (1) a PDI of at least 1.3, more preferably at least1.5, at least 1.7, or at least 2.0, and most preferably at least 2.6, upto a maximum value of 5.0, more preferably up to a maximum of 3.5, andespecially up to a maximum of 2.7; (2) a heat of fusion of 80 J/g orless; (3) an ethylene content of at least 50 weight percent; (4) a glasstransition temperature, T_(g), of less than −25° C., more preferablyless than −30° C., and/or (5) one and only one T_(m).

Further, the inventive polymers can have, alone or in combination withany other properties disclosed herein, a storage modulus, G′, such thatlog (G′) is greater than or equal to 400 kPa, preferably greater than orequal to 1.0 MPa, at a temperature of 100° C. Moreover, the inventivepolymers possess a relatively flat storage modulus as a function oftemperature in the range from 0 to 100° C. (illustrated in FIG. 6) thatis characteristic of block copolymers, and heretofore unknown for anolefin copolymer, especially a copolymer of ethylene and one or moreC₃₋₈ aliphatic α-olefins. (By the term “relatively flat” in this contextis meant that log G′ (in Pascals) decreases by less than one order ofmagnitude between 50 and 100° C., preferably between 0 and 100° C.).

The inventive interpolymers may be further characterized by athermomechanical analysis penetration depth of 1 mm at a temperature ofat least 90° C. as well as a flexural modulus of from 3 kpsi (20 MPa) to13 kpsi (90 MPa). Alternatively, the inventive interpolymers can have athermomechanical analysis penetration depth of 1 mm at a temperature ofat least 104° C. as well as a flexural modulus of at least 3 kpsi (20MPa). They may be characterized as having an abrasion resistance (orvolume loss) of less than 90 mm³. FIG. 7 shows the TMA (1 mm) versusflex modulus for the inventive polymers, as compared to other knownpolymers. The inventive polymers have significantly betterflexibility-heat resistance balance than the other polymers.

Additionally, the ethylene/α-olefin interpolymers can have a melt index,12, from 0.01 to 2000 g/10 minutes, preferably from 0.01 to 1000 g/10minutes, more preferably from 0.01 to 500 g/10 minutes, and especiallyfrom 0.01 to 100 g/10 minutes. In certain embodiments, theethylene/α-olefin interpolymers have a melt index, 12, from 0.01 to 10g/10 minutes, from 0.5 to 50 g/10 minutes, from 1 to 30 g/10 minutes,from 1 to 6 g/10 minutes or from 0.3 to 10 g/10 minutes. In certainembodiments, the melt index for the ethylene/α-olefin polymers is 1 g/10minutes, 3 g/10 minutes or 5 g/10 minutes.

The polymers can have molecular weights, M_(w), from 1,000 g/mole to5,000,000 g/mole, preferably from 1000 g/mole to 1,000,000, morepreferably from 10,000 g/mole to 500,000 g/mole, and especially from10,000 g/mole to 300,000 g/mole. The density of the inventive polymerscan be from 0.80 to 0.99 g/cm³ and preferably for ethylene containingpolymers from 0.85 g/cm³ to 0.97 g/cm³. In certain embodiments, thedensity of the ethylene/α-olefin polymers ranges from 0.860 to 0.925g/cm³ or 0.867 to 0.910 g/cm³.

The process of making the polymers has been disclosed in the followingpatent applications: U.S. Provisional Application No. 60/553,906, filedMar. 17, 2004; U.S. Provisional Application No. 60/662,937, filed Mar.17, 2005; U.S. Provisional Application No. 60/662,939, filed Mar. 17,2005; U.S. Provisional Application No. 60/566,2938, filed Mar. 17, 2005;PCT Application No. PCT/US2005/008916, filed Mar. 17, 2005; PCTApplication No. PCT/US2005/008915, filed Mar. 17, 2005; and PCTApplication No. PCT/US2005/008917, filed Mar. 17, 2005, all of which areincorporated by reference herein in their entirety. For example, onesuch method comprises contacting ethylene and optionally one or moreaddition polymerizable monomers other than ethylene under additionpolymerization conditions with a catalyst composition comprising:

the admixture or reaction product resulting from combining:

(A) a first olefin polymerization catalyst having a high comonomerincorporation index,

(B) a second olefin polymerization catalyst having a comonomerincorporation index less than 90 percent, preferably less than 50percent, most preferably less than 5 percent of the comonomerincorporation index of catalyst (A), and

(C) a chain shuttling agent.

Representative catalysts and chain shuttling agent are as follows.

Catalyst (A1) is[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl, prepared according to the teachings of WO 03/40195,2003US0204017, U.S. Ser. No. 10/429,024, filed May 2, 2003, and WO04/24740.

Catalyst (A2) is[N-(2,6-di(1-methylethyl)phenyl)amido)(2-methylphenyl)(1,2-phenylene-(6-pyridin-2-diyl)methane)]hafniumdimethyl, prepared according to the teachings of WO 03/40195,2003US0204017, U.S. Ser. No. 10/429,024, filed May 2, 2003, and WO04/24740.

Catalyst (A3) isbis[N,N′″-(2,4,6-tri(methylphenyl)amido)ethylenediamine]hafniumdibenzyl.

Catalyst (A4) isbis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)cyclohexane-1,2-diylzirconium (IV) dibenzyl, prepared substantially according to theteachings of US-A-2004/0010103.

Catalyst (B1) is1,2-bis-(3,5-di-t-butylphenylene)(1-(N-(1-methylethyl)immino)methyl)(2-oxoyl)zirconiumdibenzyl

Catalyst (B2) is1,2-bis-(3,5-di-t-butylphenylene)(1-(N-(2-methylcyclohexyl)-immino)methyl)(2-oxoyl)zirconiumdibenzyl

Catalyst (C1) is(t-butylamido)dimethyl(3-N-pyrrolyl-1,2,3,3a,7a-η-inden-1-yl)silanetitaniumdimethyl prepared substantially according to the techniques of U.S. Pat.No. 6,268,444:

Catalyst (C2) is(t-butylamido)di(4-methylphenyl)(2-methyl-1,2,3,3a,7a-η-inden-1-yl)silanetitaniumdimethyl prepared substantially according to the teachings ofUS-A-2003/004286:

Catalyst (C3) is(t-butylamido)di(4-methylphenyl)(2-methyl-1,2,3,3a,8a-η-s-indacen-1-yl)silanetitaniumdimethyl prepared substantially according to the teachings ofUS-A-2003/004286:

Catalyst (D1) is bis(dimethyldisiloxane)(indene-1-yl)zirconiumdichloride available from Sigma-Aldrich:

Shuttling Agents The shuttling agents employed include diethylzinc,di(i-butyl)zinc, di(n-hexyl)zinc, triethylaluminum, trioctylaluminum,triethylgallium, i-butylaluminum bis(dimethyl(t-butyl)siloxane),i-butylaluminum bis(di(trimethylsilyl)amide), n-octylaluminumdi(pyridine-2-methoxide), bis(n-octadecyl)i-butylaluminum,i-butylaluminum bis(di(n-pentyl)amide), n-octylaluminumbis(2,6-di-t-butylphenoxide, n-octylaluminum di(ethyl(1-naphthyl)amide),ethylaluminum bis(t-butyldimethylsiloxide), ethylaluminumdi(bis(trimethylsilyl)amide), ethylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminumbis(dimethyl(t-butyl)siloxide, ethylzinc (2,6-diphenylphenoxide), andethylzinc (t-butoxide).

Preferably, the foregoing process takes the form of a continuoussolution process for forming block copolymers, especially multi-blockcopolymers, preferably linear multi-block copolymers of two or moremonomers, more especially ethylene and a C₃₋₂₀ olefin or cycloolefin,and most especially ethylene and a C₄₋₂₀ α-olefin, using multiplecatalysts that are incapable of interconversion. That is, the catalystsare chemically distinct. Under continuous solution polymerizationconditions, the process is ideally suited for polymerization of mixturesof monomers at high monomer conversions. Under these polymerizationconditions, shuttling from the chain shuttling agent to the catalystbecomes advantaged compared to chain growth, and multi-block copolymers,especially linear multi-block copolymers are formed in high efficiency.

The inventive interpolymers may be differentiated from conventional,random copolymers, physical blends of polymers, and block copolymersprepared via sequential monomer addition, fluxional catalysts, anionicor cationic living polymerization techniques. In particular, compared toa random copolymer of the same monomers and monomer content atequivalent crystallinity or modulus, the inventive interpolymers havebetter (higher) heat resistance as measured by melting point, higher TMApenetration temperature, higher high-temperature tensile strength,and/or higher high-temperature torsion storage modulus as determined bydynamic mechanical analysis. Compared to a random copolymer containingthe same monomers and monomer content, the inventive interpolymers havelower compression set, particularly at elevated temperatures, lowerstress relaxation, higher creep resistance, higher tear strength, higherblocking resistance, faster setup due to higher crystallization(solidification) temperature, higher recovery (particularly at elevatedtemperatures), better abrasion resistance, higher retractive force, andbetter oil and filler acceptance.

The inventive interpolymers also exhibit a unique crystallization andbranching distribution relationship. That is, the inventiveinterpolymers have a relatively large difference between the tallestpeak temperature measured using CRYSTAF and DSC as a function of heat offusion, especially as compared to random copolymers containing the samemonomers and monomer level or physical blends of polymers, such as ablend of a high density polymer and a lower density copolymer, atequivalent overall density. It is believed that this unique feature ofthe inventive interpolymers is due to the unique distribution of thecomonomer in blocks within the polymer backbone. In particular, theinventive interpolymers may comprise alternating blocks of differingcomonomer content (including homopolymer blocks). The inventiveinterpolymers may also comprise a distribution in number and/or blocksize of polymer blocks of differing density or comonomer content, whichis a Schultz-Flory type of distribution. In addition, the inventiveinterpolymers also have a unique peak melting point and crystallizationtemperature profile that is substantially independent of polymerdensity, modulus, and morphology. In a preferred embodiment, themicrocrystalline order of the polymers demonstrates characteristicspherulites and lamellae that are distinguishable from random or blockcopolymers, even at PDI values that are less than 1.7, or even less than1.5, down to less than 1.3.

Moreover, the inventive interpolymers may be prepared using techniquesto influence the degree or level of blockiness. That is the amount ofcomonomer and length of each polymer block or segment can be altered bycontrolling the ratio and type of catalysts and shuttling agent as wellas the temperature of the polymerization, and other polymerizationvariables. A surprising benefit of this phenomenon is the discovery thatas the degree of blockiness is increased, the optical properties, tearstrength, and high temperature recovery properties of the resultingpolymer are improved. In particular, haze decreases while clarity, tearstrength, and high temperature recovery properties increase as theaverage number of blocks in the polymer increases. By selectingshuttling agents and catalyst combinations having the desired chaintransferring ability (high rates of shuttling with low levels of chaintermination) other forms of polymer termination are effectivelysuppressed. Accordingly, little if any β-hydride elimination is observedin the polymerization of ethylene/α-olefin comonomer mixtures accordingto embodiments of the invention, and the resulting crystalline blocksare highly, or substantially completely, linear, possessing little or nolong chain branching.

Polymers with highly crystalline chain ends can be selectively preparedin accordance with embodiments of the invention. In elastomerapplications, reducing the relative quantity of polymer that terminateswith an amorphous block reduces the intermolecular dilutive effect oncrystalline regions. This result can be obtained by choosing chainshuttling agents and catalysts having an appropriate response tohydrogen or other chain terminating agents. Specifically, if thecatalyst which produces highly crystalline polymer is more susceptibleto chain termination (such as by use of hydrogen) than the catalystresponsible for producing the less crystalline polymer segment (such asthrough higher comonomer incorporation, regio-error, or atactic polymerformation), then the highly crystalline polymer segments willpreferentially populate the terminal portions of the polymer. Not onlyare the resulting terminated groups crystalline, but upon termination,the highly crystalline polymer forming catalyst site is once againavailable for reinitiation of polymer formation. The initially formedpolymer is therefore another highly crystalline polymer segment.Accordingly, both ends of the resulting multi-block copolymer arepreferentially highly crystalline.

The ethylene α-olefin interpolymers used in the embodiments of theinvention are preferably interpolymers of ethylene with at least oneC₃-C₂₀ α-olefin. Copolymers of ethylene and a C₃-C₂₀ α-olefin areespecially preferred. The interpolymers may further comprise C₄-C₁₈diolefin and/or alkenylbenzene. Suitable unsaturated comonomers usefulfor polymerizing with ethylene include, for example, ethylenicallyunsaturated monomers, conjugated or nonconjugated dienes, polyenes,alkenylbenzenes, etc. Examples of such comonomers include C₃-C₂₀α-olefins such as propylene, isobutylene, 1-butene, 1-hexene, 1-pentene,4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, and thelike. 1-Butene and 1-octene are especially preferred. Other suitablemonomers include styrene, halo- or alkyl-substituted styrenes,vinylbenzocyclobutane, 1,4-hexadiene, 1,7-octadiene, and naphthenics(e.g., cyclopentene, cyclohexene and cyclooctene).

While ethylene/α-olefin interpolymers are preferred polymers, otherethylene/olefin polymers may also be used. Olefins as used herein referto a family of unsaturated hydrocarbon-based compounds with at least onecarbon-carbon double bond. Depending on the selection of catalysts, anyolefin may be used in embodiments of the invention. Preferably, suitableolefins are C₃-C₂₀ aliphatic and aromatic compounds containing vinylicunsaturation, as well as cyclic compounds, such as cyclobutene,cyclopentene, dicyclopentadiene, and norbornene, including but notlimited to, norbornene substituted in the 5 and 6 position with C₁-C₂₀hydrocarbyl or cyclohydrocarbyl groups. Also included are mixtures ofsuch olefins as well as mixtures of such olefins with C₄-C₄₀ diolefincompounds.

Examples of olefin monomers include, but are not limited to propylene,isobutylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, and 1-dodecene, 1-tetradecene, 1-hexadecene,1-octadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene,4-methyl-1-pentene, 4,6-dimethyl-1-heptene, 4-vinylcyclohexene,vinylcyclohexane, norbornadiene, ethylidene norbornene, cyclopentene,cyclohexene, dicyclopentadiene, cyclooctene, C₄-C₄₀ dienes, includingbut not limited to 1,3-butadiene, 1,3-pentadiene, 1,4-hexadiene,1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, other C₄-C₄₀ α-olefins, andthe like. In certain embodiments, the α-olefin is propylene, 1-butene,1-pentene, 1-hexene, 1-octene or a combination thereof. Although anyhydrocarbon containing a vinyl group potentially may be used inembodiments of the invention, practical issues such as monomeravailability, cost, and the ability to conveniently remove unreactedmonomer from the resulting polymer may become more problematic as themolecular weight of the monomer becomes too high.

The polymerization processes described herein are well suited for theproduction of olefin polymers comprising monovinylidene aromaticmonomers including styrene, o-methyl styrene, p-methyl styrene,t-butylstyrene, and the like. In particular, interpolymers comprisingethylene and styrene can be prepared by following the teachings herein.Optionally, copolymers comprising ethylene, styrene and a C₃-C₂₀ alphaolefin, optionally comprising a C₄-C₂₀ diene, having improved propertiescan be prepared.

Suitable non-conjugated diene monomers can be a straight chain, branchedchain or cyclic hydrocarbon diene having from 6 to 15 carbon atoms.Examples of suitable non-conjugated dienes include, but are not limitedto, straight chain acyclic dienes, such as 1,4-hexadiene, 1,6-octadiene,1,7-octadiene, 1,9-decadiene, branched chain acyclic dienes, such as5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene;3,7-dimethyl-1,7-octadiene and mixed isomers of dihydromyricene anddihydroocinene, single ring alicyclic dienes, such as1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene and1,5-cyclododecadiene, and multi-ring alicyclic fused and bridged ringdienes, such as tetrahydroindene, methyl tetrahydroindene,dicyclopentadiene, bicyclo-(2,2,1)-hepta-2,5-diene; alkenyl, alkylidene,cycloalkenyl and cycloalkylidene norbornenes, such as5-methylene-2-norbornene (MNB); 5-propenyl-2-norbornene,5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene,5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene, and norbornadiene.Of the dienes typically used to prepare EPDMs, the particularlypreferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene(ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2-norbornene (MNB),and dicyclopentadiene (DCPD). The especially preferred dienes are5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).

One class of desirable polymers that can be made in accordance withembodiments of the invention are elastomeric interpolymers of ethylene,a C₃-C₂₀ α-olefin, especially propylene, and optionally one or morediene monomers. Preferred α-olefins for use in this embodiment of thepresent invention are designated by the formula CH₂═CHR*, where R* is alinear or branched alkyl group of from 1 to 12 carbon atoms. Examples ofsuitable α-olefins include, but are not limited to, propylene,isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and1-octene. A particularly preferred α-olefin is propylene. The propylenebased polymers are generally referred to in the art as EP or EPDMpolymers. Suitable dienes for use in preparing such polymers, especiallymulti-block EPDM type polymers include conjugated or non-conjugated,straight or branched chain-, cyclic- or polycyclic-dienes comprisingfrom 4 to 20 carbons. Preferred dienes include 1,4-pentadiene,1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene,cyclohexadiene, and 5-butylidene-2-norbornene. A particularly preferreddiene is 5-ethylidene-2-norbornene.

Because the diene containing polymers comprise alternating segments orblocks containing greater or lesser quantities of the diene (includingnone) and α-olefin (including none), the total quantity of diene andα-olefin may be reduced without loss of subsequent polymer properties.That is, because the diene and α-olefin monomers are preferentiallyincorporated into one type of block of the polymer rather than uniformlyor randomly throughout the polymer, they are more efficiently utilizedand subsequently the crosslink density of the polymer can be bettercontrolled. Such crosslinkable elastomers and the cured products haveadvantaged properties, including higher tensile strength and betterelastic recovery.

In some embodiments, the inventive interpolymers made with two catalystsincorporating differing quantities of comonomer have a weight ratio ofblocks formed thereby from 95:5 to 5:95. The elastomeric polymersdesirably have an ethylene content of from 20 to 90 percent, a dienecontent of from 0.1 to 10 percent, and an α-olefin content of from 10 to80 percent, based on the total weight of the polymer. Furtherpreferably, the multi-block elastomeric polymers have an ethylenecontent of from 60 to 90 percent, a diene content of from 0.1 to 10percent, and an α-olefin content of from 10 to 40 percent, based on thetotal weight of the polymer. Preferred polymers are high molecularweight polymers, having a weight average molecular weight (Mw) from10,000 to about 2,500,000, preferably from 20,000 to 500,000, morepreferably from 20,000 to 350,000, and a polydispersity less than 3.5,more preferably less than 3.0, and a Mooney viscosity (ML (1+4) 125° C.)from 1 to 250. More preferably, such polymers have an ethylene contentfrom 65 to 75 percent, a diene content from 0 to 6 percent, and anα-olefin content from 20 to 35 percent.

The ethylene/α-olefin interpolymers can be functionalized byincorporating at least one functional group in its polymer structure.Exemplary functional groups may include, for example, ethylenicallyunsaturated mono- and di-functional carboxylic acids, ethylenicallyunsaturated mono- and di-functional carboxylic acid anhydrides, saltsthereof and esters thereof. Such functional groups may be grafted to anethylene/α-olefin interpolymer, or it may be copolymerized with ethyleneand an optional additional comonomer to form an interpolymer ofethylene, the functional comonomer and optionally other comonomer(s).Means for grafting functional groups onto polyethylene are described forexample in U.S. Pat. Nos. 4,762,890, 4,927,888, and 4,950,541, thedisclosures of these patents are incorporated herein by reference intheir entirety. One particularly useful functional group is malicanhydride.

The amount of the functional group present in the functionalinterpolymer can vary. The functional group can typically be present ina copolymer-type functionalized interpolymer in an amount of at leastabout 1.0 weight percent, preferably at least about 5 weight percent,and more preferably at least about 7 weight percent. The functionalgroup will typically be present in a copolymer-type functionalizedinterpolymer in an amount less than about 40 weight percent, preferablyless than about 30 weight percent, and more preferably less than about25 weight percent.

The amount of the ethylene/α-olefin interpolymer in the polymer blenddisclosed herein can be from about 5 to about 95 wt %, from about 10 toabout 90 wt %, from about 20 to about 80 wt %, from about 30 to about 70wt %, from about 10 to about 50 wt %, from about 50 to about 90 wt %,from about 60 to about 90 wt %, or from about 70 to about 90 wt % of thetotal weight of the polymer blend.

Polyolefins

The polymer blends disclosed herein can comprise at least onepolyolefin. Preferably, a suitable polyolefin should have a meltstrength (“MS”) of at least about 6 cN. In some embodiments, the MS ofthe polyolefin is at least about 7 cN, at least about 8 cN, at leastabout 9 cN, at least about 10 cN, at least about 13 cN, at least about15 cN, at least about 17 cN, or at least about 20 cN. Generally, the MSof the polyolefin is less than about 200 cN, preferably less than about150 cN, less than about 100 cN, or less than about 50 cN. Typically, thecompression set at 70° C. of such polyoelfins is great than about 50percent. In some embodiments, the compression set at 70° C. is greatthan about 60 percent, great than about 70 percent, great than about 80percent, or great than about 90 percent.

A polyolefin is a polymer derived from two or more olefins (i.e.,alkenes). An olefin (i.e., alkene) is a hydrocarbon contains at leastone carbon-carbon double bond. The olefin can be a monoene (i.e, anolefin having a single carbon-carbon double bond), diene (i.e, an olefinhaving two carbon-carbon double bonds), triene (i.e, an olefin havingthree carbon-carbon double bonds), tetraene (i.e, an olefin having fourcarbon-carbon double bonds), and other polyenes. The olefin or alkene,such as monoene, diene, triene, tetraene and other polyenes, can have 3or more carbon atoms, 4 or more carbon atoms, 6 or more carbon atoms, 8or more carbon atoms. In some embodiments, the olefin has from 3 toabout 100 carbon atoms, from 4 to about 100 carbon atoms, from 6 toabout 100 carbon atoms, from 8 to about 100 carbon atoms, from 3 toabout 50 carbon atoms, from 3 to about 25 carbon atoms, from 4 to about25 carbon atoms, from 6 to about 25 carbon atoms, from 8 to about 25carbon atoms, or from 3 to about 10 carbon atoms. In some embodiments,the olefin is a linear or branched, cyclic or acyclic, monoene havingfrom 2 to about 20 carbon atoms. In other embodiments, the alkene is adiene such as butadiene and 1,5-hexadiene. In further embodiments, atleast one of the hydrogen atoms of the alkene is substituted with analkyl or aryl. In particular embodiments, the alkene is ethylene,propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene,norbornene, 1-decene, butadiene, 1,5-hexadiene, styrene or a combinationthereof.

The amount of the polyolefin in the polymer blend can be from about 0.5to about 99 wt %, from about 1 to about 95 wt %, from about 10 to about90 wt %, from about 20 to about 80 wt %, from about 30 to about 70 wt %,from about 5 to about 50 wt %, from about 50 to about 95 wt %, fromabout 10 to about 50 wt %, from about 10 to about 30 wt %, or from about50 to about 90 wt % of the total weight of the polymer blend. In someembodiments, the amount of the polyolefin in the polymer blend can befrom about 1 to about 25 wt %, from about 5 to about 15 wt %, from about7.5 to about 12.5 wt %, or about 10 wt % of the total weight of thepolymer blend.

Any polyolefin known to a person of ordinary skill in the art may beused to prepare the polymer blend disclosed herein. The polyolefins canbe olefin homopolymers, olefin copolymers, olefin terpolymers, olefinquaterpolymers and the like, and combinations thereof.

In some embodiments, the polyolefin is an olefin homopolymer. The olefinhomopolymer can be derived from one olefin. Any olefin homopolymer knownto a person of ordinary skill in the art may be used. Non-limitingexamples of olefin homopolymers include polyethylene, polypropylene,polybutylene, polypentene-1, polyhexene-1, polyoctene-1, polydecene-1,poly-3-methylbutene-1, poly-4-methylpentene-1, polyisoprene,polybutadiene, poly-1,5-hexadiene.

In other embodiments, the olefin homopolymer is a polyethylene. Anypolyethylene known to a person of ordinary skill in the art may be usedto prepare the polymer blends disclosed herein. Non-limiting examples ofpolypropylene include ultralow density polyethylene (ULDPE), low densitypolyethylene (LDPE), linear high density low density polyethylene(LLDPE), medium density polyethylene (MDPE), high density polyethylene(HDPE), high melt strength high density polyethylene (HMS-HDPE), andultrahigh density polyethylene (UHDPE), and the like, and combinationsthereof. In some embodiments, the olefin homopolymer is a HMS-HDPE suchas Dow CONTINUUM® HDPE 2492 (available from Dow Chemical, Midland,Mich.). In other embodiments, the amount of the HMS-HDPE in the polymerblend can be from about 1 to about 25 wt %, from about 5 to about 15 wt%, from about 7.5 to about 12.5 wt %, or about 10 wt % of the totalweight of the polymer blend.

In other embodiments, the olefin homopolymer is a polypropylene. Anypolypropylene known to a person of ordinary skill in the art may be usedto prepare the polymer blends disclosed herein. Non-limiting examples ofpolypropylene include low density polypropylene (LDPP), high densitypolypropylene (HDPP), high melt strength polypropylene (HMS-PP), highimpact polypropylene (HIPP), isotactic polypropylene (iPP), syndiotacticpolypropylene (sPP) and the like, and combinations thereof. In someembodiments, the olefin homopolymer is a HMS-PP such as Dow INSPIRE®D114 (available from Dow Chemical, Midland, Mich.), PROFAX® PF814(available from Basell Polyolefins, Elkton, Md.), DAPLOY® WB130 andWB260 (available from Borealis A/S, Lyngby, Denmark). In otherembodiments, the amount of the HMS-PP in the polymer blend can be fromabout 1 to about 25 wt %, from about 5 to about 15 wt %, from about 7.5to about 12.5 wt %, or about 10 wt % of the total weight of the polymerblend.

In other embodiments, the polyolefin is an olefin copolymer. The olefincopolymer can be derived from any two different olefins. Any olefincopolymer known to a person of ordinary skill in the art may be used inthe polymer blends disclosed herein. Non-limiting examples of olefincopolymers include copolymers derived from ethylene and a monoene having3 or more carbon atoms. Non-limiting examples of the monoene having 3 ormore carbon atoms include propene; butenes (e.g., 1-butene, 2-butene andisobutene) and alkyl substituted butenes; pentenes (e.g., 1-pentene and2 pentene) and alkyl substituted pentenes (e.g., 4-methyl-1-pentene);hexenes (e.g., 1-hexene, 2-hexene and 3-hexene) and alkyl substitutedhexenes; heptenes (e.g., 1-heptene, 2-heptene and 3-heptene) and alkylsubstituted heptenes; octenes (e.g., 1-octene, 2-octene, 3-octene and4-octene) and alkyl substituted octenes; nonenes (e.g., 1-nonene,2-nonene, 3-nonene and 4-nonene) and alkyl substituted nonenes; decenes(e.g., 1-decene, 2-decene, 3-decene, 4-decene and 5-decene) and alkylsubstituted decenes; dodecenes and alkyl substituted dodecenes; andbutadiene. In some embodiments, the olefin copolymer is anethylene/alpha-olefin (EAO) copolymer or ethylene/propylene copolymer(EPM).

In other embodiments, the polyolefin is an olefin terpolymer. The olefinterpolymer can be derived from three different olefins. Any olefinterpolymer known to a person of ordinary skill in the art may be used inthe polymer blends disclosed herein. Non-limiting examples of olefinterpolymers include terpolymers derived from (i) ethylene, (ii) amonoene having 3 or more carbon atoms, and (iii) a diene. In someembodiments, the olefin terpolymer is an ethylene/alpha-olefin/dieneterpolymers (EAODM) and ethylene/propylene/diene terpolymer (EPDM).

Some of the important properties for suitable polyolefins includetensile strength, tear strength, modulus, upper service temperature,scratch and mar resistance, and others. The combination of high tensilestrength, heat resistance and processability of polypropylenehomopolymer, propylene-alpha-olefin copolymer, propylene impactcopolymer, high density polyethylene, low density polyethylene, linearlow density polyethylene and ethylene-alpha-olefin copolymer makes thesepolymers preferred blend components. Furthermore, styrenic blockcopolymers (styrene-ethylene-butene-styrene) can be blended to obtain aunique balance of elastic recovery and heat resistance (see below).

Styrenic Block Copolymers

In addition to or in place of the at least one polyolefin describedabove, the polymer blend also can comprise at least one styrenic blockcopolymer. The amount of a styrenic block copolymer in the polymer blendcan be from about 0.5 to about 99 wt %, from about 1 to about 95 wt %,from about 10 to about 90 wt %, from about 20 to about 80 wt %, fromabout 30 to about 70 wt %, from about 5 to about 50 wt %, from about 50to about 95 wt %, from about 10 to about 50 wt %, from about 10 to about30 wt %, or from about 50 to about 90 wt % of the total weight of thepolymer blend. In some embodiments, the amount of the styrenic blockcopolymer in the polymer blend can be from about 1 to about 25 wt %,from about 5 to about 15 wt %, from about 7.5 to about 12.5 wt %, orabout 10 wt % of the total weight of the polymer blend.

Generally speaking, styrenic block copolymers include at least twomonoalkenyl arene blocks, preferably two polystyrene blocks, separatedby a block of a saturated conjugated diene, preferably a saturatedpolybutadiene block. The preferred styrenic block copolymers have alinear structure, although branched or radial polymers or functionalizedblock copolymers make useful compounds. The total number averagemolecular weight of the styrenic block copolymer is preferably from30,000 to about 250,000 if the copolymer has a linear structure. Suchblock copolymers may have an average polystyrene content from 10% byweight to 40% by weight.

Suitable unsaturated block copolymers include, but are not limited to,those represented by the following formulas:A-B—R(—B-A)_(n)  Formula IorA_(x)-(BA-)_(y)-BA  Formula II

wherein each A is a polymer block comprising a vinyl aromatic monomer,preferably styrene, and each B is a polymer block comprising aconjugated diene, preferably isoprene or butadiene, and optionally avinyl aromatic monomer, preferably styrene; R is the remnant of amultifunctional coupling agent (if R is present, the block copolymer canbe a star or branched block copolymer); n is an integer from 1 to 5; xis zero or 1; and y is a real number from zero to 4.

Methods for the preparation of such block copolymers are known in theart. See, e.g., U.S. Pat. No. 5,418,290. Suitable catalysts for thepreparation of useful block copolymers with unsaturated rubber monomerunits include lithium based catalysts and especially lithium-alkyls.U.S. Pat. No. 3,595,942 describes suitable methods for hydrogenation ofblock copolymers with unsaturated rubber monomer units to from blockcopolymers with saturated rubber monomer units. The structure of thepolymers is determined by their methods of polymerization. For example,linear polymers result by sequential introduction of the desired rubbermonomer into the reaction vessel when using such initiators aslithium-alkyls or dilithiostilbene and the like, or by coupling a twosegment block copolymer with a difunctional coupling agent. Branchedstructures, on the other hand, may be obtained by the use of suitablecoupling agents having a functionality with respect to the blockcopolymers with unsaturated rubber monomer units of three or more.Coupling may be effected with multifunctional coupling agents such asdihaloalkanes or alkenes and divinyl benzene as well as with certainpolar compounds such as silicon halides, siloxanes or esters ofmonohydric alcohols with carboxylic acids. The presence of any couplingresidues in the polymer may be ignored for an adequate description ofthe block copolymers.

Suitable block copolymers having unsaturated rubber monomer unitsinclude, but are not limited to, styrene-butadiene (SB),styrene-ethylene/butadiene (SEB), styrene-isoprene (SI),styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS),α-methylstyrene-butadiene-α-methylstyrene andα-methylstyrene-isoprene-α-methylstyrene.

The styrenic portion of the block copolymer is preferably a polymer orinterpolymer of styrene and its analogs and homologs includingα-methylstyrene and ring-substituted styrenes, particularlyring-methylated styrenes. The preferred styrenics are styrene andα-methylstyrene, and styrene is particularly preferred.

Block copolymers with unsaturated rubber monomer units may comprisehomopolymers of butadiene or isoprene or they may comprise copolymers ofone or both of these two dienes with a minor amount of styrenic monomer.In some embodiments, the block copolymers are derived from (i) a C₃₋₂₀olefin substituted with an alkyl or aryl group (e.g., 4-methyl-1-penteneand styrene) and (ii) a diene (e.g. butadiene, 1,5-hexadiene,1,7-octadiene and 1,9-decadiene). A non-limiting example of such olefincopolymer includes styrene-butadiene-styrene (SBS) block copolymer.

Preferred block copolymers with saturated rubber monomer units compriseat least one segment of a styrenic unit and at least one segment of anethylene-butene or ethylene-propylene copolymer. Preferred examples ofsuch block copolymers with saturated rubber monomer units includestyrene/ethylene-butene copolymers, styrene/ethylene-propylenecopolymers, styrene/ethylene-butene/styrene (SEBS) copolymers,styrene/ethylene-propylene/styrene (SEPS) copolymers.

Hydrogenation of block copolymers with unsaturated rubber monomer unitsis preferably effected by use of a catalyst comprising the reactionproducts of an aluminum alkyl compound with nickel or cobaltcarboxylates or alkoxides under such conditions as to substantiallycompletely hydrogenate at least 80 percent of the aliphatic double bondswhile hydrogenating no more than 25 percent of the styrenic aromaticdouble bonds. Preferred block copolymers are those where at least 99percent of the aliphatic double bonds are hydrogenated while less than 5percent of the aromatic double bonds are hydrogenated.

The proportion of the styrenic blocks is generally between 8 and 65percent by weight of the total weight of the block copolymer.Preferably, the block copolymers contain from 10 to 35 weight percent ofstyrenic block segments and from 90 to 65 weight percent of rubbermonomer block segments, based on the total weight of the blockcopolymer.

The average molecular weights of the individual blocks may vary withincertain limits. In most instances, the styrenic block segments will havenumber average molecular weights in the range of 5,000 to 125,000,preferably from 7,000 to 60,000 while the rubber monomer block segmentswill have average molecular weights in the range of 10,000 to 300,000,preferably from 30,000 to 150,000. The total average molecular weight ofthe block copolymer is typically in the range of 25,000 to 250,000,preferably from 35,000 to 200,000.

Further, the various block copolymers suitable for use in embodiments ofthe invention may be modified by graft incorporation of minor amounts offunctional groups, such as, for example, maleic anhydride by any of themethods well known in the art.

Suitable block copolymers include, but are not limited to, thosecommercially available, such as, KRATON™ supplied by KRATON Polymers LLCin Houston, Tex. and VECTOR™ supplied by Dexco Polymers, L.P. inHouston, Tex.

Additives

Optionally, the polymer blends disclosed herein can comprise at leastone additive for the purposes of improving and/or controlling theprocessibility, appearance, physical, chemical, and/or mechanicalproperties of the polymer blends. In some embodiments, the polymerblends do not comprise an additive. Any plastics additive known to aperson of ordinary skill in the art may be used in the polymer blendsdisclosed herein. Non-limiting examples of suitable additives includeslip agents, anti-blocking agents, plasticizers, oils, antioxidants, UVstabilizers, colorants or pigments, fillers, lubricants, antifoggingagents, flow aids, coupling agents, crosslinking agents, nucleatingagents, surfactants, solvents, flame retardants, antistatic agents, andcombinations thereof. The total amount of the additives can range fromabout greater than 0 to about 80%, from about 0.001% to about 70%, fromabout 0.01% to about 60%, from about 0.1% to about 50%, from about 1% toabout 40%, or from about 10% to about 50% of the total weight of thepolymer blend. Some polymer additives have been described in ZweifelHans et al., “Plastics Additives Handbook,” Hanser Gardner Publications,Cincinnati, Ohio, 5th edition (2001), which is incorporated herein byreference in its entirety.

In some embodiments, the polymer blends disclosed herein comprise a slipagent. In other embodiments, the polymer blends disclosed herein do notcomprise a slip agent. Slip is the sliding of film surfaces over eachother or over some other substrates. The slip performance of films canbe measured by ASTM D 1894, Static and Kinetic Coefficients of Frictionof Plastic Film and Sheeting, which is incorporated herein by reference.In general, the slip agent can convey slip properties by modifying thesurface properties of films; and reducing the friction between layers ofthe films and between the films and other surfaces with which they comeinto contact.

Any slip agent known to a person of ordinary skill in the art may beadded to the polymer blends disclosed herein. Non-limiting examples ofthe slip agents include primary amides having about 12 to about 40carbon atoms (e.g., erucamide, oleamide, stearamide and behenamide);secondary amides having about 18 to about 80 carbon atoms (e.g., stearylerucamide, behenyl erucamide, methyl erucamide and ethyl erucamide);secondary-bis-amides having about 18 to about 80 carbon atoms (e.g.,ethylene-bis-stearamide and ethylene-bis-oleamide); and combinationsthereof. In a particular embodiment, the slip agent for the polymerblends disclosed herein is an amide represented by Formula (I) below:

wherein each of R¹ and R² is independently H, alkyl, cycloalkyl,alkenyl, cycloalkenyl or aryl; and R³ is alkyl or alkenyl, each havingabout 11 to about 39 carbon atoms, about 13 to about 37 carbon atoms,about 15 to about 35 carbon atoms, about 17 to about 33 carbon atoms orabout 19 to about 33 carbon atoms. In some embodiments, R³ is alkyl oralkenyl, each having at least 19 to about 39 carbon atoms. In otherembodiments, R³ is pentadecyl, heptadecyl, nonadecyl, heneicosanyl,tricosanyl, pentacosanyl, heptacosanyl, nonacosanyl, hentriacontanyl,tritriacontanyl, nonatriacontanyl or a combination thereof. In furtherembodiments, R³ is pentadecenyl, heptadecenyl, nonadecenyl,heneicosanenyl, tricosanenyl, pentacosanenyl, heptacosanenyl,nonacosanenyl, hentriacontanenyl, tritriacontanenyl, nonatriacontanenylor a combination thereof.

In a further embodiment, the slip agent for the polymer blends disclosedherein is an amide represented by Formula (II) below:CH₃—(CH₂)_(m)—(CH═CH)_(p)—(CH₂)_(n)—C(═O)—NR¹R²  (II)wherein each of m and n is independently an integer between about 1 andabout 37; p is an integer between 0 and 3; each of R¹ and R² isindependently H, alkyl, cycloalkyl, alkenyl, cycloalkenyl or aryl; andthe sum of m, n and p is at least 8. In some embodiments, each of R andR of Formulae (I) and (II) is an alkyl group containing between 1 andabout 40 carbon atoms or an alkenyl group containing between 2 and about40 carbon atoms. In further embodiments, each of R¹ and R² of Formulae(I) and (II) is H. In certain embodiments, the sum of m, n and p is atleast 18.

The amide of Formula (I) or (II) can be prepared by the reaction of anamine of formula H—NR¹R² where each of R¹ and R² is independently H,alkyl, cycloalkyl, alkenyl, cycloalkenyl or aryl with a carboxylic acidhaving a formula of R³—CO₂H or CH₃—(CH₂)_(m)—(CH═CH)_(p)—(CH₂)_(n)—CO₂Hwhere R³ is alkyl or alkenyl, each having at least 19 to about 39 carbonatoms; each of m and n is independently an integer between about 1 andabout 37; and p is 0 or 1. The amine of formula H—NR¹R² can be ammonia(i.e., each of R¹ and R² is H), a primary amine (i.e., R¹ is alkyl,cycloalkyl, alkenyl, cycloalkenyl or aryl and R² is H) or a secondaryamine (i.e., each of R¹ and R² is independently alkyl, cycloalkyl,alkenyl, cycloalkenyl or aryl). Some non-limiting examples of primaryamine include methylamine, ethylamine, octadecylamine, behenylamine,tetracosanylamine, hexacosanylamine, octacosanylamine, triacontylamine,dotriacontylamine, tetratriacontylamine, tetracontylamine,cyclohexylamine and combinations thereof. Some non-limiting examples ofsecondary amine include dimethylamine, diethylamine, dihexadecylamine,dioctadecylamine, dieicosylamine, didocosylamine, dicetylamine,distearylamine, diarachidylamine, dibehenylamine, dihydrogenated tallowamine, and combinations thereof. The primary amines and secondary aminescan be prepared by methods known to a person of ordinary skill in theart or obtained from a commercial supplier such as Aldrich Chemicals,Milwaukee, Wis.; ICC Chemical Corporation, New York, N.Y.; Chemos GmbH,Regenstauf, Germany; ABCR GmbH & Co. KG, Karlsruhe, Germany; and AcrosOrganics, Geel, Belgium.

The primary amines or secondary amines may be prepared by reductiveamination reaction. The reductive amination is the process by whichammonia or a primary amine is condensed with an aldehyde or a ketone toform the corresponding imine which is subsequently reduced to an amine.The subsequent reduction of imine to amine may be accomplished byreacting the imine with hydrogen and a suitable hydrogenation catalystsuch as Raney Nickel and platinum oxide, aluminum-mercury amalgam, or ahydride such as lithium aluminum hydride, sodium cyanoborohydride, andsodium borohydride. The reductive amination is described in U.S. Pat.No. 3,187,047; and articles by Haskelberg, “Aminative Reduction ofKetones,” J. Am. Chem. Soc., 70 (1948) 2811-2; Mastagli et al., “Studyof the Aminolysis of Some Ketones and Aldehydes,” Bull. soc. chim.France (1950) 1045-8; B. J. Hazzard, Practical Handbook of OrganicChemistry, Addison-Wesley Publishing Co., Inc., pp. 458-9 and 686(1973); and Alexander et al., “A Low Pressure Reductive AlkylationMethod for the Conversion of Ketones to Primary Amines,” J. Am. Chem.Soc., 70, 1315-6 (1948). The above U.S. patent and articles areincorporated herein by reference.

Non-limiting examples of the carboxylic acid include straight-chainsaturated fatty acids such as tetradecanoic acid, pentadecanoic acid,hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoicacid, eicosanoic acid, heneicosanic acid, docosanoic acid, tricosanoicacid, tetracosanoic acid, pentacosanoic acid, hexacosanoic acid,heptacosanoic acid, octacosanoic acid, nonacosanoic acid, triacontanoicacid, hentriacontanoic acid, dotriacontanoic acid, tetratriacontanoicacid, hexatriacontanoic acid, octatriacontanoic acid and tetracontanoicacid; branched-chain saturated fatty acids such as16-methylheptadecanoic acid, 3-methyl-2-octylynonanoic acid,2,3-dimethyloctadecanoic acid, 2-methyltetracosanoic acid,11-methyltetracosanoic acid, 2-pentadecyl-heptadecanoic acid;unsaturated fatty acids such as trans-3-octadecenoic acid,trans-11-eicosenoic acid, 2-methyl-2-eicosenoic acid,2-methyl-2-hexacosenoic acid, β-eleostearic acid, α-parinaric acid,9-nonadecenoic acid, and 22-tricosenoic acid, oleic acid and erucicacid. The carboxylic acids can be prepared by methods known to a personof ordinary skill in the art or obtained from a commercial supplier suchas Aldrich Chemicals, Milwaukee, Wis.; ICC Chemical Corporation, NewYork, N.Y.; Chemos GmbH, Regenstauf, Germany; ABCR GmbH & Co. KG,Karlsruhe, Germany; and Acros Organics, Geel, Belgium. Some knownmethods for the preparation of the carboxylic acids include theoxidation of the corresponding primary alcohols with an oxidation agentsuch as metal chromates, metal dichromates and potassium permanganate.The oxidation of alcohols to carboxylic acids is described in Carey etal., “Advance Organic Chemistry, Part B: Reactions and Synthesis,”Plenum Press, New York, 2nd Edition, pages 481-491 (1983), which isincorporated herein by reference.

The amidation reaction can take place in a solvent that is not reactivetoward the carboxylic acid. Non-limiting examples of suitable solventsinclude ethers (i.e., diethyl ether and tetrahydrofuran), ketones (suchas acetone and methyl ethyl ketone), acetonitrile, dimethyl sulfoxide,dimethyl formamide and the like. The amidation reaction can be promotedby a base catalyst. Non-limiting examples of the base catalyst includeinorganic bases such as sodium hydroxide, potassium hydroxide, sodiumcarbonate, potassium carbonate, sodium hydrogen carbonate, sodiumacetate, ammonium acetate, and the like, metal alkoxides such as sodiummethoxide, sodium ethoxide, and the like, amines such as triethylamine,diisopropylethylamine, and the like. In some embodiments, the catalystis an amine or a metal alkoxide.

In some embodiments, the slip agent is a primary amide with a saturatedaliphatic group having between 18 and about 40 carbon atoms (e.g.,stearamide and behenamide). In other embodiments, the slip agent is aprimary amide with an unsaturated aliphatic group containing at leastone carbon-carbon double bond and between 18 and about 40 carbon atoms(e.g., erucamide and oleamide). In further embodiments, the slip agentis a primary amide having at least 20 carbon atoms. In furtherembodiments, the slip agent is erucamide, oleamide, stearamide,behenamide, ethylene-bis-stearamide, ethylene-bis-oleamide, stearylerucamide, behenyl erucamide or a combination thereof. In a particularembodiment, the slip agent is erucamide. In further embodiments, theslip agent is commercially available having a trade name such as ATMER™SA from Uniqema, Everberg, Belgium; ARMOSLIP® from Akzo Nobel PolymerChemicals, Chicago, Ill.; KEMAMIDE® from Witco, Greenwich, Conn.; andCRODAMIDE® from Croda, Edison, N.J. Where used, the amount of the slipagent in the polymer blend can be from about greater than 0 to about 3wt %, from about 0.0001 to about 2 wt %, from about 0.001 to about 1 wt%, from about 0.001 to about 0.5 wt % or from about 0.05 to about 0.25wt % of the total weight of the polymer blend. Some slip agents havebeen described in Zweifel Hans et al., “Plastics Additives Handbook,”Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 8,pages 601-608 (2001), which is incorporated herein by reference.

Optionally, the polymer blends disclosed herein can comprise ananti-blocking agent. In some embodiments, the polymer blends disclosedherein do not comprise an anti-blocking agent. The anti-blocking agentcan be used to prevent the undesirable adhesion between touching layersof articles made from the polymer blends, particularly under moderatepressure and heat during storage, manufacture or use. Any anti-blockingagent known to a person of ordinary skill in the art may be added to thepolymer blends disclosed herein. Non-limiting examples of anti-blockingagents include minerals (e.g., clays, chalk, and calcium carbonate),synthetic silica gel (e.g., SYLOBLOC® from Grace Davison, Columbia,Md.), natural silica (e.g., SUPER FLOSS® from Celite Corporation, SantaBarbara, Calif.), talc (e.g., OPTIBLOC® from Luzenac, Centennial,Colo.), zeolites (e.g., SIPERNAT® from Degussa, Parsippany, N.J.),aluminosilicates (e.g., SILTON® from Mizusawa Industrial Chemicals,Tokyo, Japan), limestone (e.g., CARBOREX® from Omya, Atlanta, Ga.),spherical polymeric particles (e.g., EPOSTAR®, poly(methyl methacrylate)particles from Nippon Shokubai, Tokyo, Japan and TOSPEARL®, siliconeparticles from GE Silicones, Wilton, Conn.), waxes, amides (e.g.erucamide, oleamide, stearamide, behenamide, ethylene-bis-stearamide,ethylene-bis-oleamide, stearyl erucamide and other slip agents),molecular sieves, and combinations thereof. The mineral particles canlower blocking by creating a physical gap between articles, while theorganic anti-blocking agents can migrate to the surface to limit surfaceadhesion. Where used, the amount of the anti-blocking agent in thepolymer blend can be from about greater than 0 to about 3 wt %, fromabout 0.0001 to about 2 wt %, from about 0.001 to about 1 wt %, or fromabout 0.001 to about 0.5 wt % of the total weight of the polymer blend.Some anti-blocking agents have been described in Zweifel Hans et al.,“Plastics Additives Handbook,” Hanser Gardner Publications, Cincinnati,Ohio, 5th edition, Chapter 7, pages 585-600 (2001), which isincorporated herein by reference.

Optionally, the polymer blends disclosed herein can comprise aplasticizer. In general, a plasticizer is a chemical that can increasethe flexibility and lower the glass transition temperature of polymers.Any plasticizer known to a person of ordinary skill in the art may beadded to the polymer blends disclosed herein. Non-limiting examples ofplasticizers include mineral oils, abietates, adipates, alkylsulfonates, azelates, benzoates, chlorinated paraffins, citrates,epoxides, glycol ethers and their esters, glutarates, hydrocarbon oils,isobutyrates, oleates, pentaerythritol derivatives, phosphates,phthalates, esters, polybutenes, ricinoleates, sebacates, sulfonamides,tri- and pyromellitates, biphenyl derivatives, stearates, difurandiesters, fluorine-containing plasticizers, hydroxybenzoic acid esters,isocyanate adducts, multi-ring aromatic compounds, natural productderivatives, nitriles, siloxane-based plasticizers, tar-based products,thioeters and combinations thereof. Where used, the amount of theplasticizer in the polymer blend can be from greater than 0 to about 15wt %, from about 0.5 to about 10 wt %, or from about 1 to about 5 wt %of the total weight of the polymer blend. Some plasticizers have beendescribed in George Wypych, “Handbook of Plasticizers,” ChemTecPublishing, Toronto-Scarborough, Ontario (2004), which is incorporatedherein by reference.

In some embodiments, the polymer blends disclosed herein optionallycomprise an antioxidant that can prevent the oxidation of polymercomponents and organic additives in the polymer blends. Any antioxidantknown to a person of ordinary skill in the art may be added to thepolymer blends disclosed herein. Non-limiting examples of suitableantioxidants include aromatic or hindered amines such as alkyldiphenylamines, phenyl-α-naphthylamine, alkyl or aralkyl substitutedphenyl-α-naphthylamine, alkylated p-phenylene diamines,tetramethyl-diaminodiphenylamine and the like; phenols such as2,6-di-t-butyl-4-methylphenol;1,3,5-trimethyl-2,4,6-tris(3′,5′-di-t-butyl-4′-hydroxybenzyl)benzene;tetrakis[(methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane(e.g., IRGANOX™ 1010, from Ciba Geigy, New York); acryloyl modifiedphenols; octadecyl-3,5-di-t-butyl-4-hydroxycinnamate (e.g., IRGANOX™1076, commercially available from Ciba Geigy); phosphites andphosphonites; hydroxylamines; benzofuranone derivatives; andcombinations thereof. Where used, the amount of the antioxidant in thepolymer blend can be from about greater than 0 to about 5 wt %, fromabout 0.0001 to about 2.5 wt %, from about 0.001 to about 1 wt %, orfrom about 0.001 to about 0.5 wt % of the total weight of the polymerblend. Some antioxidants have been described in Zweifel Hans et al.,“Plastics Additives Handbook,” Hanser Gardner Publications, Cincinnati,Ohio, 5th edition, Chapter 1, pages 1-140 (2001), which is incorporatedherein by reference.

In other embodiments, the polymer blends disclosed herein optionallycomprise an UV stabilizer that may prevent or reduce the degradation ofthe polymer blends by UV radiations. Any UV stabilizer known to a personof ordinary skill in the art may be added to the polymer blendsdisclosed herein. Non-limiting examples of suitable UV stabilizersinclude benzophenones, benzotriazoles, aryl esters, oxanilides, acrylicesters, formamidines, carbon black, hindered amines, nickel quenchers,hindered amines, phenolic antioxidants, metallic salts, zinc compoundsand combinations thereof. Where used, the amount of the UV stabilizer inthe polymer blend can be from about greater than 0 to about 5 wt %, fromabout 0.01 to about 3 wt %, from about 0.1 to about 2 wt %, or fromabout 0.1 to about 1 wt % of the total weight of the polymer blend. SomeUV stabilizers have been described in Zweifel Hans et al., “PlasticsAdditives Handbook,” Hanser Gardner Publications, Cincinnati, Ohio, 5thedition, Chapter 2, pages 141-426 (2001), which is incorporated hereinby reference.

In further embodiments, the polymer blends disclosed herein optionallycomprise a colorant or pigment that can change the look of the polymerblends to human eyes. Any colorant or pigment known to a person ofordinary skill in the art may be added to the polymer blends disclosedherein. Non-limiting examples of suitable colorants or pigments includeinorganic pigments such as metal oxides such as iron oxide, zinc oxide,and titanium dioxide, mixed metal oxides, carbon black, organic pigmentssuch as anthraquinones, anthanthrones, azo and monoazo compounds,arylamides, benzimidazolones, BONA lakes, diketopyrrolo-pyrroles,dioxazines, disazo compounds, diarylide compounds, flavanthrones,indanthrones, isoindolinones, isoindolines, metal complexes, monoazosalts, naphthols, b-naphthols, naphthol AS, naphthol lakes, perylenes,perinones, phthalocyanines, pyranthrones, quinacridones, andquinophthalones, and combinations thereof. Where used, the amount of thecolorant or pigment in the polymer blend can be from about greater than0 to about 10 wt %, from about 0.1 to about 5 wt %, or from about 0.25to about 2 wt % of the total weight of the polymer blend. Some colorantshave been described in Zweifel Hans et al., “Plastics AdditivesHandbook,” Hanser Gardner Publications, Cincinnati, Ohio, 5th edition,Chapter 15, pages 813-882 (2001), which is incorporated herein byreference.

Optionally, the polymer blends disclosed herein can comprise a fillerwhich can be used to adjust, inter alia, volume, weight, costs, and/ortechnical performance. Any filler known to a person of ordinary skill inthe art may be added to the polymer blends disclosed herein.Non-limiting examples of suitable fillers include talc, calciumcarbonate, chalk, calcium sulfate, clay, kaolin, silica, glass, fumedsilica, mica, wollastonite, feldspar, aluminum silicate, calciumsilicate, alumina, hydrated alumina such as alumina trihydrate, glassmicrosphere, ceramic microsphere, thermoplastic microsphere, barite,wood flour, glass fibers, carbon fibers, marble dust, cement dust,magnesium oxide, magnesium hydroxide, antimony oxide, zinc oxide, bariumsulfate, titanium dioxide, titanates and combinations thereof. In someembodiments, the filler is barium sulfate, talc, calcium carbonate,silica, glass, glass fiber, alumina, titanium dioxide, or a mixturethereof. In other embodiments, the filler is talc, calcium carbonate,barium sulfate, glass fiber or a mixture thereof. Where used, the amountof the filler in the polymer blend can be from about greater than 0 toabout 80 wt %, from about 0.1 to about 60 wt %, from about 0.5 to about40 wt %, from about 1 to about 30 wt %, or from about 10 to about 40 wt% of the total weight of the polymer blend. Some fillers have beendisclosed in U.S. Pat. No. 6,103,803 and Zweifel Hans et al., “PlasticsAdditives Handbook,” Hanser Gardner Publications, Cincinnati, Ohio, 5thedition, Chapter 17, pages 901-948 (2001), both of which areincorporated herein by reference.

Optionally, the polymer blends disclosed herein can comprise alubricant. In general, the lubricant can be used, inter alia, to modifythe rheology of the molten polymer blends, to improve the surface finishof molded articles, and/or to facilitate the dispersion of fillers orpigments. Any lubricant known to a person of ordinary skill in the artmay be added to the polymer blends disclosed herein. Non-limitingexamples of suitable lubricants include fatty alcohols and theirdicarboxylic acid esters, fatty acid esters of short-chain alcohols,fatty acids, fatty acid amides, metal soaps, oligomeric fatty acidesters, fatty acid esters of long-chain alcohols, montan waxes,polyethylene waxes, polypropylene waxes, natural and synthetic paraffinwaxes, fluoropolymers and combinations thereof. Where used, the amountof the lubricant in the polymer blend can be from about greater than 0to about 5 wt %, from about 0.1 to about 4 wt %, or from about 0.1 toabout 3 wt % of the total weight of the polymer blend. Some suitablelubricants have been disclosed in Zweifel Hans et al., “PlasticsAdditives Handbook,” Hanser Gardner Publications, Cincinnati, Ohio, 5thedition, Chapter 5, pages 511-552 (2001), both of which are incorporatedherein by reference.

Optionally, the polymer blends disclosed herein can comprise anantistatic agent. Generally, the antistatic agent can increase theconductivity of the polymer blends and to prevent static chargeaccumulation. Any antistatic agent known to a person of ordinary skillin the art may be added to the polymer blends disclosed herein.Non-limiting examples of suitable antistatic agents include conductivefillers (e.g., carbon black, metal particles and other conductiveparticles), fatty acid esters (e.g., glycerol monostearate), ethoxylatedalkylamines, diethanolamides, ethoxylated alcohols, alkylsulfonates,alkylphosphates, quaternary ammonium salts, alkylbetaines andcombinations thereof. Where used, the amount of the antistatic agent inthe polymer blend can be from about greater than 0 to about 5 wt %, fromabout 0.01 to about 3 wt %, or from about 0.1 to about 2 wt % of thetotal weight of the polymer blend. Some suitable antistatic agents havebeen disclosed in Zweifel Hans et al., “Plastics Additives Handbook,”Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 10,pages 627-646 (2001), both of which are incorporated herein byreference.

Optionally, the polymer blends may be crosslinked, partially orcompletely. When crosslinking is desired, the polymer blends disclosedherein comprise a cross-linking agent that can be used to effect thecross-linking of the polymer blends, thereby increasing their modulusand stiffness, among other things. Any cross-linking agent known to aperson of ordinary skill in the art may be added to the polymer blendsdisclosed herein. Non-limiting examples of suitable cross-linking agentsinclude organic peroxides (e.g., alkyl peroxides, aryl peroxides,peroxyesters, peroxycarbonates, diacylperoxides, peroxyketals, andcyclic peroxides) and silanes (e.g., vinyltrimethoxysilane,vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane,vinyltriacetoxysilane, vinylmethyldimethoxysilane, and3-methacryloyloxypropyltrimethoxysilane). Where used, the amount of thecross-linking agent in the polymer blend can be from about greater than0 to about 20 wt %, from about 0.1 to about 15 wt %, or from about 1 toabout 10 wt % of the total weight of the polymer blend. Some suitablecross-linking agents have been disclosed in Zweifel Hans et al.,“Plastics Additives Handbook,” Hanser Gardner Publications, Cincinnati,Ohio, 5th edition, Chapter 14, pages 725-812 (2001), both of which areincorporated herein by reference.

The cross-linking of the polymer blends can also be initiated by anyradiation means known in the art, including, but not limited to,electron-beam irradiation, beta irradiation, gamma irradiation, coronairradiation, and UV radiation with or without cross-linking catalyst.U.S. patent application Ser. No. 10/086,057 (published as US2002/0132923A1) and U.S. Pat. No. 6,803,014 disclose electron-beam irradiationmethods that can be used in embodiments of the invention.

Irradiation may be accomplished by the use of high energy, ionizingelectrons, ultra violet rays, X-rays, gamma rays, beta particles and thelike and combination thereof. Preferably, electrons are employed up to70 megarads dosages. The irradiation source can be any electron beamgenerator operating in a range of about 150 kilovolts to about 6megavolts with a power output capable of supplying the desired dosage.The voltage can be adjusted to appropriate levels which may be, forexample, 100,000, 300,000, 1,000,000 or 2,000,000 or 3,000,000 or6,000,000 or higher or lower. Many other apparati for irradiatingpolymeric materials are known in the art. The irradiation is usuallycarried out at a dosage between about 3 megarads to about 35 megarads,preferably between about 8 to about 20 megarads. Further, theirradiation can be carried out conveniently at room temperature,although higher and lower temperatures, for example 0° C. to about 60°C., may also be employed. Preferably, the irradiation is carried outafter shaping or fabrication of the article. Also, in a preferredembodiment, the ethylene interpolymer which has been incorporated with apro-rad additive is irradiated with electron beam radiation at about 8to about 20 megarads.

Crosslinking can be promoted with a crosslinking catalyst, and anycatalyst that will provide this function can be used. Suitable catalystsgenerally include organic bases, carboxylic acids, and organometalliccompounds including organic titanates and complexes or carboxylates oflead, cobalt, iron, nickel, zinc and tin. Dibutyltindilaurate,dioctyltinmaleate, dibutyltindiacetate, dibutyltindioctoate, stannousacetate, stannous octoate, lead naphthenate, zinc caprylate, cobaltnaphthenate; and the like. Tin carboxylate, especiallydibutyltindilaurate and dioctyltinmaleate, are particularly effectivefor this invention. The catalyst (or mixture of catalysts) is present ina catalytic amount, typically between about 0.015 and about 0.035 phr.

Representative pro-rad additives include, but are not limited to, azocompounds, organic peroxides and polyfunctional vinyl or allyl compoundssuch as, for example, triallyl cyanurate, triallyl isocyanurate,pentaerthritol tetramethacrylate, glutaraldehyde, ethylene glycoldimethacrylate, diallyl maleate, dipropargyl maleate, dipropargylmonoallyl cyanurate, dicumyl peroxide, di-tert-butyl peroxide, t-butylperbenzoate, benzoyl peroxide, cumene hydroperoxide, t-butyl peroctoate,methyl ethyl ketone peroxide, 2,5-dimethyl-2,5-di(t-butyl peroxy)hexane,lauryl peroxide, tert-butyl peracetate, azobisisobutyl nitrite and thelike and combination thereof. Preferred pro-rad additives for use in thepresent invention are compounds which have poly-functional (i.e. atleast two) moieties such as C═C, C═N or C═O.

At least one pro-rad additive can be introduced to the ethyleneinterpolymer by any method known in the art. However, preferably thepro-rad additive(s) is introduced via a masterbatch concentratecomprising the same or different base resin as the ethyleneinterpolymer. Preferably, the pro-rad additive concentration for themasterbatch is relatively high e.g., about 25 weight percent (based onthe total weight of the concentrate).

The at least one pro-rad additive is introduced to the ethylene polymerin any effective amount. Preferably, the at least one pro-rad additiveintroduction amount is from about 0.001 to about 5 weight percent, morepreferably from about 0.005 to about 2.5 weight percent and mostpreferably from about 0.015 to about 1 weight percent (based on thetotal weight of the ethylene interpolymer.

In addition to electron-beam irradiation, crosslinking can also beeffected by UV irradiation. U.S. Pat. No. 6,709,742 discloses across-linking method by UV irradiation which can be used in embodimentsof the invention. The method comprises mixing a photoinitiator, with orwithout a photocrosslinker, with a polymer before, during, or after afiber is formed and then exposing the fiber with the photoinitiator tosufficient UV radiation to crosslink the polymer to the desired level.The photoinitiators used in the practice of the invention are aromaticketones, e.g., benzophenones or monoacetals of 1,2-diketones. Theprimary photoreaction of the monacetals is the homolytic cleavage of theα-bond to give acyl and dialkoxyalkyl radicals. This type of α-cleavageis known as a Norrish Type I reaction which is more fully described inW. Horspool and D. Armesto, Organic Photochemistry: A ComprehensiveTreatment, Ellis Horwood Limited, Chichester, England, 1992; J. Kopecky,Organic Photochemistry: A Visual Approach, VCH Publishers, Inc., NewYork, N.Y. 1992; N. J. Turro, et al., Acc. Chem. Res., 1972, 5, 92; andJ. T. Banks, et al., J. Am. Chem. Soc., 1993, 115, 2473. The synthesisof monoacetals of aromatic 1,2 diketones, Ar—CO—C(OR)₂—Ar′ is describedin U.S. Pat. No. 4,190,602 and Ger. Offen. 2,337,813. The preferredcompound from this class is 2,2-dimethoxy-2-phenylacetophenone,C₆H₅—CO—C(OCH₃)₂—C₆H₅, which is commercially available from Ciba-Geigyas Irgacure 651. Examples of other aromatic ketones useful in thepractice of this invention as photoinitiators are Irgacure 184, 369,819, 907 and 2959, all available from Ciba-Geigy.

In one embodiment of the invention, the photoinitiator is used incombination with a photocrosslinker. Any photocrosslinker that will uponthe generation of free radicals, link two or more polyolefin backbonestogether through the formation of covalent bonds with the backbones canbe used in this invention. Preferably these photocrosslinkers arepolyfunctional, i.e., they comprise two or more sites that uponactivation will form a covalent bond with a site on the backbone of thecopolymer. Representative photocrosslinkers include, but are not limitedto polyfunctional vinyl or allyl compounds such as, for example,triallyl cyanurate, triallyl isocyanurate, pentaerthritoltetramethacrylate, ethylene glycol dimethacrylate, diallyl maleate,dipropargyl maleate, dipropargyl monoallyl cyanurate and the like.Preferred photocrosslinkers for use in the present invention arecompounds which have polyfunctional (i.e. at least two) moieties.Particularly preferred photocrosslinkers are triallycyanurate (TAC) andtriallylisocyanurate (TAIC).

Certain compounds act as both a photoinitiator and a photocrosslinker inthe practice of this invention. These compounds are characterized by theability to generate two or more reactive species (e.g., free radicals,carbenes, nitrenes, etc.) upon exposure to UV-light and to subsequentlycovalently bond with two polymer chains. Any compound that can performthese two functions can be used in the practice of this invention, andrepresentative compounds include the sulfonyl azides described in U.S.Pat. Nos. 6,211,302 and 6,284,842.

In another embodiment of this invention, the copolymer is subjected tosecondary crosslinking, i.e., crosslinking other than and in addition tophotocrosslinking. In this embodiment, the photoinitiator is used eitherin combination with a nonphotocrosslinker, e.g., a silane, or thecopolymer is subjected to a secondary crosslinking procedure, e.g,exposure to E-beam radiation. Representative examples of silanecrosslinkers are described in U.S. Pat. No. 5,824,718, and crosslinkingthrough exposure to E-beam radiation is described in U.S. Pat. Nos.5,525,257 and 5,324,576. The use of a photocrosslinker in thisembodiment is optional

At least one photoadditive, i.e., photoinitiator and optionalphotocrosslinker, can be introduced to the copolymer by any method knownin the art. However, preferably the photoadditive(s) is (are) introducedvia a masterbatch concentrate comprising the same or different baseresin as the copolymer. Preferably, the photoadditive concentration forthe masterbatch is relatively high e.g., about 25 weight percent (basedon the total weight of the concentrate).

The at least one photoadditive is introduced to the copolymer in anyeffective amount. Preferably, the at least one photoadditiveintroduction amount is from about 0.001 to about 5, more preferably fromabout 0.005 to about 2.5 and most preferably from about 0.015 to about1, wt % (based on the total weight of the copolymer).

The photoinitiator(s) and optional photocrosslinker(s) can be addedduring different stages of the fiber or film manufacturing process. Ifphotoadditives can withstand the extrusion temperature, a polyolefinresin can be mixed with additives before being fed into the extruder,e.g., via a masterbatch addition. Alternatively, additives can beintroduced into the extruder just prior the slot die, but in this casethe efficient mixing of components before extrusion is important. Inanother approach, polyolefin fibers can be drawn without photoadditives,and a photoinitiator and/or photocrosslinker can be applied to theextruded fiber via a kiss-roll, spray, dipping into a solution withadditives, or by using other industrial methods for post-treatment. Theresulting fiber with photoadditive(s) is then cured via electromagneticradiation in a continuous or batch process. The photo additives can beblended with the polyolefin using conventional compounding equipment,including single and twin-screw extruders.

The power of the electromagnetic radiation and the irradiation time arechosen so as to allow efficient crosslinking without polymer degradationand/or dimensional defects. The preferred process is described in EP 0490 854 B1. Photoadditive(s) with sufficient thermal stability is (are)premixed with a polyolefin resin, extruded into a fiber, and irradiatedin a continuous process using one energy source or several units linkedin a series. There are several advantages to using a continuous processcompared with a batch process to cure a fiber or sheet of a knittedfabric which are collected onto a spool.

Irradiation may be accomplished by the use of UV-radiation. Preferably,UV-radiation is employed up to the intensity of 100 J/cm². Theirradiation source can be any UV-light generator operating in a range ofabout 50 watts to about 25000 watts with a power output capable ofsupplying the desired dosage. The wattage can be adjusted to appropriatelevels which may be, for example, 1000 watts or 4800 watts or 6000 wattsor higher or lower. Many other apparati for UV-irradiating polymericmaterials are known in the art. The irradiation is usually carried outat a dosage between about 3 J/cm² to about 500 J/scm^(2,), preferablybetween about 5 J/cm² to about 100 J/cm². Further, the irradiation canbe carried out conveniently at room temperature, although higher andlower temperatures, for example 0° C. to about 60° C., may also beemployed. The photocrosslinking process is faster at highertemperatures. Preferably, the irradiation is carried out after shapingor fabrication of the article. In a preferred embodiment, the copolymerwhich has been incorporated with a photoadditive is irradiated withUV-radiation at about 10 J/cm² to about 50 J/cm².

Preparation of the Polymer Blends

The ingredients of the polymer blends, i.e., the ethylene/α-olefininterpolymer, the polyolefin and the optional additives, can be mixed orblended using methods known to a person of ordinary skill in the art,preferably methods that can provide a substantially homogeneousdistribution of the polyolefin and/or the additives in theethylene/α-olefin interpolymer. Non-limiting examples of suitableblending methods include melt blending, solvent blending, extruding, andthe like.

In some embodiments, the ingredients of the polymer blends are meltblended by a method as described by Guerin et al. in U.S. Pat. No.4,152,189. First, all solvents, if there are any, are removed from theingredients by heating to an appropriate elevated temperature of about100° C. to about 200° C. or about 150° C. to about 175° C. at a pressureof about 5 torr (667 Pa) to about 10 torr (1333 Pa). Next, theingredients are weighed into a vessel in the desired proportions and thepolymer blend is formed by heating the contents of the vessel to amolten state while stirring.

In other embodiments, the ingredients of the polymer blends areprocessed using solvent blending. First, the ingredients of the desiredpolymer blend are dissolved in a suitable solvent and the mixture isthen mixed or blended. Next, the solvent is removed to provide thepolymer blend.

In further embodiments, physical blending devices that providedispersive mixing, distributive mixing, or a combination of dispersiveand distributive mixing can be useful in preparing homogenous blends.Both batch and continuous methods of physical blending can be used.Non-limiting examples of batch methods include those methods usingBRABENDER® mixing equipments (e.g., BRABENDER PREP CENTER®, availablefrom C. W. Brabender Instruments, Inc., South Hackensack, N.J.) orBANBURY® internal mixing and roll milling (available from FarrelCompany, Ansonia, Conn.) equipment. Non-limiting examples of continuousmethods include single screw extruding, twin screw extruding, diskextruding, reciprocating single screw extruding, and pin barrel singlescrew extruding. In some embodiments, the additives can be added into anextruder through a feed hopper or feed throat during the extrusion ofthe ethylene/α-olefin interpolymer, the polyolefin or the polymer blend.The mixing or blending of polymers by extrusion has been described in C.Rauwendaal, “Polymer Extrusion”, Hanser Publishers, New York, N.Y.,pages 322-334 (1986), which is incorporated herein by reference.

When one or more additives are required in the polymer blends, thedesired amounts of the additives can be added in one charge or multiplecharges to the ethylene/α-olefin interpolymer, the polyolefin or thepolymer blend. Furthermore, the addition can take place in any order. Insome embodiments, the additives are first added and mixed or blendedwith the ethylene/α-olefin interpolymer and then the additive-containinginterpolymer is blended with the polyolefin. In other embodiments, theadditives are first added and mixed or blended with the polyolefin andthen the additive-containing polyolefin is blended with theethylene/α-olefin interpolymer. In further embodiments, theethylene/α-olefin interpolymer is blended with the polyolefin first andthen the additives are blended with the polymer blend. Polymer blendscan also be performed at the fabrication equipment as dry blends (nopre-compounding required).

Alternatively, master batches containing high concentrations of theadditives can be used. In general, master batches can be prepared byblending either the ethylene/α-olefin interpolymer, the polyolefin orthe polymer blend with high concentrations of additives. The masterbatches can have additive concentrations from about 1 to about 50 wt %,from about 1 to about 40 wt %, from about 1 to about 30 wt %, or fromabout 1 to about 20 wt % of the total weight of the polymer blend. Themaster batches can then be added to the polymer blends in an amountdetermined to provide the desired additive concentrations in the endproducts. In some embodiments, the master batch contains a slip agent,an anti-blocking agent, a plasticizer, an antioxidant, a UV stabilizer,a colorant or pigment, a filler, a lubricant, an antifogging agent, aflow aid, a coupling agent, a cross-linking agent, a nucleating agent, asurfactant, a solvent, a flame retardant, an antistatic agent, or acombination thereof. In other embodiment, the master batch contains aslip agent, an anti-blocking agent or a combination thereof. In otherembodiment, the master batch contains a slip agent.

Applications of the Polymer Blends

The polymer blends disclosed herein can be used to manufacture durablearticles for the automotive, construction, medical, food and beverage,electrical, appliance, business machine, and consumer markets. In someembodiments, the polymer blends are used to manufacture flexible durableparts or articles selected from toys, grips, soft touch handles, bumperrub strips, floorings, auto floor mats, wheels, casters, furniture andappliance feet, tags, seals, gaskets such as static and dynamic gaskets,automotive doors, bumper fascia, grill components, rocker panels, hoses,linings, office supplies, seals, liners, diaphragms, tubes, lids,stoppers, plunger tips, delivery systems, kitchen wares, shoes, shoebladders and shoe soles. In other embodiments, the polymer blends can beused to manufacture durable parts or articles that require a hightensile strength and low compression set. In further embodiments, thepolymer blends can be used to manufacture durable parts or articles thatrequire a high upper service temperature and low modulus.

The polymer blends can be used to prepare these durable parts orarticles with known polymer processes such as extrusion (e.g., sheetextrusion and profile extrusion); molding (e.g., injection molding,rotational molding, and blow molding); fiber spinning; and blown filmand cast film processes. In general, extrusion is a process by which apolymer is propelled continuously along a screw through regions of hightemperature and pressure where it is melted and compacted, and finallyforced through a die. The extruder can be a single screw extruder, amultiple screw extruder, a disk extruder or a ram extruder. The die canbe a film die, blown film die, sheet die, pipe die, tubing die orprofile extrusion die. The extrusion of polymers has been described inC. Rauwendaal, “Polymer Extrusion”, Hanser Publishers, New York, N.Y.(1986); and M. J. Stevens, “Extruder Principals and Operation,”Ellsevier Applied Science Publishers, New York, N.Y. (1985), both ofwhich are incorporated herein by reference in their entirety.

Injection molding is also widely used for manufacturing a variety ofplastic parts for various applications. In general, injection molding isa process by which a polymer is melted and injected at high pressureinto a mold, which is the inverse of the desired shape, to form parts ofthe desired shape and size. The mold can be made from metal, such assteel and aluminum. The injection molding of polymers has been describedin Beaumont et al., “Successful Injection Molding: Process, Design, andSimulation,” Hanser Gardner Publications, Cincinnati, Ohio (2002), whichis incorporated herein by reference in its entirety.

Molding is generally a process by which a polymer is melted and led intoa mold, which is the inverse of the desired shape, to form parts of thedesired shape and size. Molding can be pressureless orpressure-assisted. The molding of polymers is described in Hans-GeorgElias “An Introduction to Plastics,” Wiley-VCH, Weinhei, Germany, pp.161-165 (2003), which is incorporated herein by reference.

Rotational molding is a process generally used for producing hollowplastic products. By using additional post-molding operations, complexcomponents can be produced as effectively as other molding and extrusiontechniques. Rotational molding differs from other processing methods inthat the heating, melting, shaping, and cooling stages all occur afterthe polymer is placed in the mold, therefore no external pressure isapplied during forming. The rotational molding of polymers has beendescribed in Glenn Beall, “Rotational Molding: Design, Materials &Processing,” Hanser Gardner Publications, Cincinnati, Ohio (1998), whichis incorporated herein by reference in its entirety.

Blow molding can be used for making hollow plastics containers. Theprocess includes placing a softened polymer in the center of a mold,inflating the polymer against the mold walls with a blow pin, andsolidifying the product by cooling. There are three general types ofblow molding: extrusion blow molding, injection blow molding, andstretch blow molding. Injection blow molding can be used to processpolymers that cannot be extruded. Stretch blow molding can be used fordifficult to blow crystalline and crystallizable polymers such aspolypropylene. The blow molding of polymers has been described in NormanC. Lee, “Understanding Blow Molding,” Hanser Gardner Publications,Cincinnati, Ohio (2000), which is incorporated herein by reference inits entirety.

The following examples are presented to exemplify embodiments of theinvention. All numerical values are approximate. When numerical rangesare given, it should be understood that embodiments outside the statedranges may still fall within the scope of the invention. Specificdetails described in each example should not be construed as necessaryfeatures of the invention.

EXAMPLES

Testing Methods

In the examples that follow, the following analytical techniques areemployed:

GPC Method for Samples 1-4 and A-C

An automated liquid-handling robot equipped with a heated needle set to160° C. is used to add enough 1,2,4-trichlorobenzene stabilized with 300ppm Ionol to each dried polymer sample to give a final concentration of30 mg/mL. A small glass stir rod is placed into each tube and thesamples are heated to 160° C. for 2 hours on a heated, orbital-shakerrotating at 250 rpm. The concentrated polymer solution is then dilutedto 1 mg/ml using the automated liquid-handling robot and the heatedneedle set to 160° C.

A Symyx Rapid GPC system is used to determine the molecular weight datafor each sample. A Gilson 350 pump set at 2.0 ml/min flow rate is usedto pump helium-purged 1,2-dichlorobenzene stabilized with 300 ppm Ionolas the mobile phase through three Plgel 10 micrometer (μm) Mixed B 300mm×7.5 mm columns placed in series and heated to 160° C. A Polymer LabsELS 1000 Detector is used with the Evaporator set to 250° C., theNebulizer set to 165° C., and the nitrogen flow rate set to 1.8 SLM at apressure of 60-80 psi (400-600 kPa) N₂. The polymer samples are heatedto 160° C. and each sample injected into a 250 μl loop using theliquid-handling robot and a heated needle. Serial analysis of thepolymer samples using two switched loops and overlapping injections areused. The sample data is collected and analyzed using Symyx Epoch™software. Peaks are manually integrated and the molecular weightinformation reported uncorrected against a polystyrene standardcalibration curve.

Standard CRYSTAF Method

Branching distributions are determined by crystallization analysisfractionation (CRYSTAF) using a CRYSTAF 200 unit commercially availablefrom PolymerChar, Valencia, Spain. The samples are dissolved in 1,2,4trichlorobenzene at 160° C. (0.66 mg/mL) for 1 hr and stabilized at 95°C. for 45 minutes. The sampling temperatures range from 95 to 30° C. ata cooling rate of 0.2° C./min. An infrared detector is used to measurethe polymer solution concentrations. The cumulative solubleconcentration is measured as the polymer crystallizes while thetemperature is decreased. The analytical derivative of the cumulativeprofile reflects the short chain branching distribution of the polymer.

The CRYSTAF peak temperature and area are identified by the peakanalysis module included in the CRYSTAF Software (Version 2001.b,PolymerChar, Valencia, Spain). The CRYSTAF peak finding routineidentifies a peak temperature as a maximum in the dW/dT curve and thearea between the largest positive inflections on either side of theidentified peak in the derivative curve. To calculate the CRYSTAF curve,the preferred processing parameters are with a temperature limit of 70°C. and with smoothing parameters above the temperature limit of 0.1, andbelow the temperature limit of 0.3.

DSC Standard Method (Excluding Samples 1-4 and A-C)

Differential Scanning Calorimetry results are determined using a TAImodel Q1000 DSC equipped with an RCS cooling accessory and anautosampler. A nitrogen purge gas flow of 50 ml/min is used. The sampleis pressed into a thin film and melted in the press at about 175° C. andthen air-cooled to room temperature (25° C.). 3-10 mg of material isthen cut into a 6 mm diameter disk, accurately weighed, placed in alight aluminum pan (ca 50 mg), and then crimped shut. The thermalbehavior of the sample is investigated with the following temperatureprofile. The sample is rapidly heated to 180° C. and held isothermal for3 minutes in order to remove any previous thermal history. The sample isthen cooled to −40° C. at 10° C./min cooling rate and held at −40° C.for 3 minutes. The sample is then heated to 150° C. at 10° C./min.heating rate. The cooling and second heating curves are recorded.

The DSC melting peak is measured as the maximum in heat flow rate (W/g)with respect to the linear baseline drawn between −30° C. and end ofmelting. The heat of fusion is measured as the area under the meltingcurve between −30° C. and the end of melting using a linear baseline.

GPC Method (Excluding Samples 1-4 and A-C)

The gel permeation chromatographic system consists of either a PolymerLaboratories Model PL-210 or a Polymer Laboratories Model PL-220instrument. The column and carousel compartments are operated at 140° C.Three Polymer Laboratories 10-micron Mixed-B columns are used. Thesolvent is 1,2,4 trichlorobenzene. The samples are prepared at aconcentration of 0.1 grams of polymer in 50 milliliters of solventcontaining 200 ppm of butylated hydroxytoluene (BHT). Samples areprepared by agitating lightly for 2 hours at 160° C. The injectionvolume used is 100 microliters and the flow rate is 1.0 ml/minute.

Calibration of the GPC column set is performed with 21 narrow molecularweight distribution polystyrene standards with molecular weights rangingfrom 580 to 8,400,000, arranged in 6 “cocktail” mixtures with at least adecade of separation between individual molecular weights. The standardsare purchased from Polymer Laboratories (Shropshire, UK). Thepolystyrene standards are prepared at 0.025 grams in 50 milliliters ofsolvent for molecular weights equal to or greater than 1,000,000, and0.05 grams in 50 milliliters of solvent for molecular weights less than1,000,000. The polystyrene standards are dissolved at 80° C. with gentleagitation for 30 minutes. The narrow standards mixtures are run firstand in order of decreasing highest molecular weight component tominimize degradation. The polystyrene standard peak molecular weightsare converted to polyethylene molecular weights using the followingequation (as described in Williams and Ward, J. Polym. Sci., Polym.Let., 6, 621 (1968)): M_(polyethylene)=0.431(M_(polystyrene)).

Polyethylene equivalent molecular weight calculations are performedusing Viscotek TriSEC software Version 3.0.

Compression Set

Compression set is measured according to ASTM D 395. The sample isprepared by stacking 25.4 mm diameter round discs of 3.2 mm, 2.0 mm, and0.25 mm thickness until a total thickness of 12.7 mm is reached. Thediscs are cut from 12.7 cm×12.7 cm compression molded plaques moldedwith a hot press under the following conditions: zero pressure for 3 minat 190° C., followed by 86 MPa for 2 min at 190° C., followed by coolinginside the press with cold running water at 86 MPa.

Density

Samples for density measurement are prepared according to ASTM D 1928.Measurements are made within one hour of sample pressing using ASTMD792, Method B.

Flexural/Secant Modulus/Storage Modulus

Samples are compression molded using ASTM D 1928. Flexural and 2 percentsecant moduli are measured according to ASTM D-790. Storage modulus ismeasured according to ASTM D 5026-01 or equivalent technique.

Optical Properties

Films of 0.4 mm thickness are compression molded using a hot press(Carver Model #4095-4PR1001R). The pellets are placed betweenpolytetrafluoroethylene sheets, heated at 190° C. at 55 psi (380 kPa)for 3 min, followed by 1.3 MPa for 3 min, and then 2.6 MPa for 3 min.The film is then cooled in the press with running cold water at 1.3 MPafor 1 min. The compression molded films are used for opticalmeasurements, tensile behavior, recovery, and stress relaxation.

Clarity is measured using BYK Gardner Haze-gard as specified in ASTM D1746.

45° gloss is measured using BYK Gardner Glossmeter Microgloss 45° asspecified in ASTM D-2457

Internal haze is measured using BYK Gardner Haze-gard based on ASTM D1003 Procedure A. Mineral oil is applied to the film surface to removesurface scratches.

Mechanical Properties—Tensile, Hysteresis, and Tear

Stress-strain behavior in uniaxial tension is measured using ASTM D 1708microtensile specimens. Samples are stretched with an Instron at 500%min⁻¹ at 21° C. Tensile strength and elongation at break are reportedfrom an average of 5 specimens.

100% and 300% Hysteresis is determined from cyclic loading to 100% and300% strains using ASTM D 1708 microtensile specimens with an Instron™instrument. The sample is loaded and unloaded at 267% min⁻¹ for 3 cyclesat 21° C. Cyclic experiments at 300% and 80° C. are conducted using anenvironmental chamber. In the 80° C. experiment, the sample is allowedto equilibrate for 45 minutes at the test temperature before testing. Inthe 21° C., 300% strain cyclic experiment, the retractive stress at 150%strain from the first unloading cycle is recorded. Percent recovery forall experiments are calculated from the first unloading cycle using thestrain at which the load returned to the base line. The percent recoveryis defined as:${\%\quad{Recovery}} = {\frac{ɛ_{f} - ɛ_{s}}{ɛ_{f}} \times 100}$where ε_(f) is the strain taken for cyclic loading and ε_(s) is thestrain where the load returns to the baseline during the 1^(st)unloading cycle.

Stress relaxation is measured at 50 percent strain and 37° C. for 12hours using an Instron™ instrument equipped with an environmentalchamber. The gauge geometry was 76 mm×25 mm×0.4 mm. After equilibratingat 37° C. for 45 min in the environmental chamber, the sample wasstretched to 50% strain at 333% min⁻¹. Stress was recorded as a functionof time for 12 hours. The percent stress relaxation after 12 hours wascalculated using the formula:${\%\quad{Stress}\quad{Relaxation}} = {\frac{L_{0} - L_{12}}{L_{0}} \times 100}$where L₀ is the load at 50% strain at 0 time and L₁₂ is the load at 50percent strain after 12 hours.

Tensile notched tear experiments are carried out on samples having adensity of 0.88 g/cc or less using an Instron™ instrument. The geometryconsists of a gauge section of 76 mm×13 mm×0.4 mm with a 2 mm notch cutinto the sample at half the specimen length. The sample is stretched at508 mm min⁻¹ at 21° C. until it breaks. The tear energy is calculated asthe area under the stress-elongation curve up to strain at maximum load.An average of at least 3 specimens are reported.

TMA

Thermal Mechanical Analysis (Penetration Temperature) is conducted on 30mm diameter×3.3 mm thick, compression molded discs, formed at 180° C.and 10 MPa molding pressure for 5 minutes and then air quenched. Theinstrument used is a TMA 7, brand available from Perkin-Elmer. In thetest, a probe with 1.5 mm radius tip (P/N N519-0416) is applied to thesurface of the sample disc with IN force. The temperature is raised at5° C./min from 25° C. The probe penetration distance is measured as afunction of temperature. The experiment ends when the probe haspenetrated 1 mm into the sample.

DMA

Dynamic Mechanical Analysis (DMA) is measured on compression moldeddisks formed in a hot press at 180° C. at 10 MPa pressure for 5 minutesand then water cooled in the press at 90° C./min. Testing is conductedusing an ARES controlled strain rheometer (TA instruments) equipped withdual cantilever fixtures for torsion testing.

A 1.5 mm plaque is pressed and cut in a bar of dimensions 32×12 mm. Thesample is clamped at both ends between fixtures separated by 10 mm (gripseparation ΔL) and subjected to successive temperature steps from −100°C. to 200° C. (5° C. per step). At each temperature the torsion modulusG′ is measured at an angular frequency of 10 rad/s, the strain amplitudebeing maintained between 0.1 percent and 4 percent to ensure that thetorque is sufficient and that the measurement remains in the linearregime.

An initial static force of 10 g is maintained (auto-tension mode) toprevent slack in the sample when thermal expansion occurs. As aconsequence, the grip separation ΔL increases with the temperature,particularly above the melting or softening point of the polymer sample.The test stops at the maximum temperature or when the gap between thefixtures reaches 65 mm.

Melt Index

Melt index, or I₂, is measured in accordance with ASTM D 1238, Condition190° C./2.16 kg. Melt index, or I₁₀ is also measured in accordance withASTM D 1238, Condition 190° C./10 kg.

ATREF

Analytical temperature rising elution fractionation (ATREF) analysis isconducted according to the method described in U.S. Pat. No. 4,798,081and Wilde, L.; Ryle, T. R.; Knobeloch, D. C.; Peat, I. R.; Determinationof Branching Distributions in Polyethylene and Ethylene Copolymers, J.Polym. Sci., 20, 441-455 (1982), which are incorporated by referenceherein in their entirety. The composition to be analyzed is dissolved intrichlorobenzene and allowed to crystallize in a column containing aninert support (stainless steel shot) by slowly reducing the temperatureto 20° C. at a cooling rate of 0.1° C./min. The column is equipped withan infrared detector. An ATREF chromatogram curve is then generated byeluting the crystallized polymer sample from the column by slowlyincreasing the temperature of the eluting solvent (trichlorobenzene)from 20 to 120° C. at a rate of 1.5° C./min.

¹³C NMR Analysis

The samples are prepared by adding approximately 3 g of a 50/50 mixtureof tetrachloroethane-d 2/orthodichlorobenzene to 0.4 g sample in a 10 mmNMR tube. The samples are dissolved and homogenized by heating the tubeand its contents to 150° C. The data are collected using a JEOL ECLIPSE™400 MHz spectrometer or a Varian Unity PLUS™ 400 MHz spectrometer,corresponding to a ¹³C resonance frequency of 100.5 MHz. The data areacquired using 4000 transients per data file with a 6 second pulserepetition delay. To achieve minimum signal-to-noise for quantitativeanalysis, multiple data files are added together. The spectral width is25,000 Hz with a minimum file size of 32K data points. The samples areanalyzed at 130° C. in a 10 mm broad band probe. The comonomerincorporation is determined using Randall's triad method (Randall, J.C.; JMS-Rev. Macromol. Chem. Phys., C29, 201-317 (1989), which isincorporated by reference herein in its entirety.

Polymer Fractionation by TREF

Large-scale TREF fractionation is carried by dissolving 15-20 g ofpolymer in 2 liters of 1,2,4-trichlorobenzene (TCB) by stirring for 4hours at 160° C. The polymer solution is forced by 15 psig (100 kPa)nitrogen onto a 3 inch by 4 foot (7.6 cm×12 cm) steel column packed witha 60:40 (v:v) mix of 30-40 mesh (600-425 μm) spherical, technicalquality glass beads (available from Potters Industries, HC 30 Box 20,Brownwood, Tex., 76801) and stainless steel, 0.028″ (0.7 mm) diametercut wire shot (available from Pellets, Inc. 63 Industrial Drive, NorthTonawanda, N.Y., 14120). The column is immersed in a thermallycontrolled oil jacket, set initially to 160° C. The column is firstcooled ballistically to 125° C., then slow cooled to 20° C. at 0.04° C.per minute and held for one hour. Fresh TCB is introduced at about 65ml/min while the temperature is increased at 0.167° C. per minute.

Approximately 2000 ml portions of eluant from the preparative TREFcolumn are collected in a 16 station, heated fraction collector. Thepolymer is concentrated in each fraction using a rotary evaporator untilabout 50 to 100 ml of the polymer solution remains. The concentratedsolutions are allowed to stand overnight before adding excess methanol,filtering, and rinsing (approx. 300-500 ml of methanol including thefinal rinse). The filtration step is performed on a 3 position vacuumassisted filtering station using 5.0 μm polytetrafluoroethylene coatedfilter paper (available from Osmonics Inc., Cat# Z50WP04750). Thefiltrated fractions are dried overnight in a vacuum oven at 60° C. andweighed on an analytical balance before further testing.

Melt Strength

Melt Strength (MS) is measured by using a capillary rheometer fittedwith a 2.1 mm diameter, 20:1 die with an entrance angle of approximately45 degrees. After equilibrating the samples at 190° C. for 10 minutes,the piston is run at a speed of 1 inch/minute (2.54 cm/minute). Thestandard test temperature is 190° C. The sample is drawn uniaxially to aset of accelerating nips located 100 mm below the die with anacceleration of 2.4 mm/sec 2. The required tensile force is recorded asa function of the take-up speed of the nip rolls. The maximum tensileforce attained during the test is defined as the melt strength. In thecase of polymer melt exhibiting draw resonance, the tensile force beforethe onset of draw resonance was taken as melt strength. The meltstrength is recorded in centiNewtons (“cN”).

Catalysts

The term “overnight”, if used, refers to a time of approximately 16-18hours, the term “room temperature”, refers to a temperature of 20-25°C., and the term “mixed alkanes” refers to a commercially obtainedmixture of C₆₋₉ aliphatic hydrocarbons available under the tradedesignation Isopar E®, from ExxonMobil Chemical Company. In the eventthe name of a compound herein does not conform to the structuralrepresentation thereof, the structural representation shall control. Thesynthesis of all metal complexes and the preparation of all screeningexperiments were carried out in a dry nitrogen atmosphere using dry boxtechniques. All solvents used were HPLC grade and were dried beforetheir use.

MMAO refers to modified methylalumoxane, a triisobutylaluminum modifiedmethylalumoxane available commercially from Akzo-Noble Corporation.

The preparation of catalyst (B1) is conducted as follows.

a) Preparation of(1-methylethyl)(2-hydroxy-3,5-di(t-butyl)phenyl)methylimine

3,5-Di-t-butylsalicylaldehyde (3.00 g) is added to 10 mL ofisopropylamine. The solution rapidly turns bright yellow. After stirringat ambient temperature for 3 hours, volatiles are removed under vacuumto yield a bright yellow, crystalline solid (97 percent yield).

b) Preparation of1,2-bis-(3,5-di-t-butylphenylene)(1-(N-(1-methylethyl)immino)methyl)(2-oxoyl)zirconiumdibenzyl

A solution of (1-methylethyl)(2-hydroxy-3,5-di(t-butyl)phenyl)imine (605mg, 2.2 mmol) in 5 mL toluene is slowly added to a solution ofZr(CH₂Ph)₄ (500 mg, 1.1 mmol) in 50 mL toluene. The resulting darkyellow solution is stirred for 30 min. Solvent is removed under reducedpressure to yield the desired product as a reddish-brown solid.

The preparation of catalyst (B2) is conducted as follows.

a) Preparation of(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)imine

2-Methylcyclohexylamine (8.44 mL, 64.0 mmol) is dissolved in methanol(90 mL), and di-t-butylsalicaldehyde (10.00 g, 42.67 mmol) is added. Thereaction mixture is stirred for three hours and then cooled to −25° C.for 12 hrs. The resulting yellow solid precipitate is collected byfiltration and washed with cold methanol (2×15 mL), and then dried underreduced pressure. The yield is 11.17 g of a yellow solid. ¹H NMR isconsistent with the desired product as a mixture of isomers.

b) Preparation ofbis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconium dibenzyl

A solution of(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)imine (7.63g, 23.2 mmol) in 200 mL toluene is slowly added to a solution ofZr(CH₂Ph)₄ (5.28 g, 11.6 mmol) in 600 mL toluene. The resulting darkyellow solution is stirred for 1 hour at 25° C. The solution is dilutedfurther with 680 mL toluene to give a solution having a concentration of0.00783 M.

Cocatalyst 1 A mixture of methyldi(C₁₄₋₁₈ alkyl)ammonium salts oftetrakis(pentafluorophenyl)borate (here-in-after armeenium borate),prepared by reaction of a long chain trialkylamine (Armeen™ M2HT,available from Akzo-Nobel, Inc.), HCl and Li[B(C₆F₅)₄], substantially asdisclosed in U.S. Pat. No. 5,919,9883, Ex. 2.

Cocatalyst 2 Mixed C₁₄₋₁₈ alkyldimethylammonium salt ofbis(tris(pentafluorophenyl)-alumane)-2-undecylimidazolide, preparedaccording to U.S. Pat. No. 6,395,671, Ex. 16.

Shuttling Agents The shuttling agents employed include diethylzinc (DEZ,SA1), di(i-butyl)zinc (SA2), di(n-hexyl)zinc (SA3), triethylaluminum(TEA, SA4), trioctylaluminum (SA5), triethylgallium (SA6),i-butylaluminum bis(dimethyl(t-butyl)siloxane) (SA7), i-butylaluminumbis(di(trimethylsilyl)amide) (SA8), n-octylaluminumdi(pyridine-2-methoxide) (SA9), bis(n-octadecyl)i-butylaluminum (SA10),i-butylaluminum bis(di(n-pentyl)amide) (SA11), n-octylaluminumbis(2,6-di-t-butylphenoxide) (SA12), n-octylaluminumdi(ethyl(1-naphthyl)amide) (SA13), ethylaluminumbis(t-butyldimethylsiloxide) (SA14), ethylaluminumdi(bis(trimethylsilyl)amide) (SA 15), ethylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide) (SA16), n-octylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide) (SA17), n-octylaluminumbis(dimethyl(t-butyl)siloxide (SA18), ethylzinc (2,6-diphenylphenoxide)(SA19), and ethylzinc (t-butoxide) (SA20).

Examples 1-4, Comparative A-C

General High Throughput Parallel Polymerization Conditions

Polymerizations are conducted using a high throughput, parallelpolymerization reactor (PPR) available from Symyx technologies, Inc. andoperated substantially according to U.S. Pat. Nos. 6,248,540, 6,030,917,6,362,309, 6,306,658, and 6,316,663. Ethylene copolymerizations areconducted at 130° C. and 200 psi (1.4 MPa) with ethylene on demand using1.2 equivalents of cocatalyst 1 based on total catalyst used (1.1equivalents when MMAO is present). A series of polymerizations areconducted in a parallel pressure reactor (PPR) contained of 48individual reactor cells in a 6×8 array that are fitted with apre-weighed glass tube. The working volume in each reactor cell is 6000μL. Each cell is temperature and pressure controlled with stirringprovided by individual stirring paddles. The monomer gas and quench gasare plumbed directly into the PPR unit and controlled by automaticvalves. Liquid reagents are robotically added to each reactor cell bysyringes and the reservoir solvent is mixed alkanes. The order ofaddition is mixed alkanes solvent (4 ml), ethylene, 1-octene comonomer(1 ml), cocatalyst 1 or cocatalyst 1/MMAO mixture, shuttling agent, andcatalyst or catalyst mixture. When a mixture of cocatalyst 1 and MMAO ora mixture of two catalysts is used, the reagents are premixed in a smallvial immediately prior to addition to the reactor. When a reagent isomitted in an experiment, the above order of addition is otherwisemaintained. Polymerizations are conducted for approximately 1-2 minutes,until predetermined ethylene consumptions are reached. After quenchingwith CO, the reactors are cooled and the glass tubes are unloaded. Thetubes are transferred to a centrifuge/vacuum drying unit, and dried for12 hours at 60° C. The tubes containing dried polymer are weighed andthe difference between this weight and the tare weight gives the netyield of polymer. Results are contained in Table 1. In Table 1 andelsewhere in the application, comparative compounds are indicated by anasterisk (*).

Examples 1-4 demonstrate the synthesis of linear block copolymers by thepresent invention as evidenced by the formation of a very narrow MWD,essentially monomodal copolymer when DEZ is present and a bimodal, broadmolecular weight distribution product (a mixture of separately producedpolymers) in the absence of DEZ. Due to the fact that Catalyst (A1) isknown to incorporate more octene than Catalyst (B1), the differentblocks or segments of the resulting copolymers of the invention aredistinguishable based on branching or density. TABLE 1 Cat. (A1) Cat(B1) Cocat MMAO shuttling Ex. (μmol) (μmol) (μmol) (μmol) agent (μmol)Yield (g) Mn Mw/Mn hexyls¹ A* 0.06 — 0.066 0.3 — 0.1363 300502 3.32 — B*— 0.1 0.110 0.5 — 0.1581 36957 1.22 2.5 C* 0.06 0.1 0.176 0.8 — 0.203845526 5.30² 5.5 1 0.06 0.1 0.192 — DEZ (8.0) 0.1974 28715 1.19 4.8 20.06 0.1 0.192 — DEZ (80.0) 0.1468 2161 1.12 14.4 3 0.06 0.1 0.192 — TEA(8.0) 0.208  22675 1.71 4.6 4 0.06 0.1 0.192 — TEA (80.0) 0.1879 33381.54 9.4¹C₆ or higher chain content per 1000 carbons²Bimodal molecular weight distribution

It may be seen the polymers produced according to the invention have arelatively narrow polydispersity (Mw/Mn) and larger block-copolymercontent (trimer, tetramer, or larger) than polymers prepared in theabsence of the shuttling agent.

Further characterizing data for the polymers of Table 1 are determinedby reference to the figures. More specifically DSC and ATREF resultsshow the following:

The DSC curve for the polymer of Example 1 shows a 115.7° C. meltingpoint (Tm) with a heat of fusion of 158.1 J/g. The corresponding CRYSTAFcurve shows the tallest peak at 34.5° C. with a peak area of 52.9percent. The difference between the DSC Tm and the Tcrystaf is 81.2° C.

The DSC curve for the polymer of Example 2 shows a peak with a 109.7° C.melting point (Tm) with a heat of fusion of 214.0 J/g. The correspondingCRYSTAF curve shows the tallest peak at 46.2° C. with a peak area of57.0 percent. The difference between the DSC Tm and the Tcrystaf is63.5° C.

The DSC curve for the polymer of Example 3 shows a peak with a 120.7° C.melting point (Tm) with a heat of fusion of 160.1 J/g. The correspondingCRYSTAF curve shows the tallest peak at 66.1° C. with a peak area of71.8 percent. The difference between the DSC Tm and the Tcrystaf is54.6° C.

The DSC curve for the polymer of Example 4 shows a peak with a 104.5° C.melting point (Tm) with a heat of fusion of 170.7 J/g. The correspondingCRYSTAF curve shows the tallest peak at 30° C. with a peak area of 18.2percent. The difference between the DSC Tm and the Tcrystaf is 74.5° C.

The DSC curve for Comparative Example A* shows a 90.0° C. melting point(Tm) with a heat of fusion of 86.7 J/g. The corresponding CRYSTAF curveshows the tallest peak at 48.5° C. with a peak area of 29.4 percent.Both of these values are consistent with a resin that is low in density.The difference between the DSC Tm and the Tcrystaf is 41.8° C.

The DSC curve for Comparative Example B* shows a 129.8° C. melting point(Tm) with a heat of fusion of 237.0 J/g. The corresponding CRYSTAF curveshows the tallest peak at 82.4° C. with a peak area of 83.7 percent.Both of these values are consistent with a resin that is high indensity. The difference between the DSC Tm and the Tcrystaf is 47.4° C.

The DSC curve for Comparative Example C* shows a 125.3° C. melting point(Tm) with a heat of fusion of 143.0 J/g. The corresponding CRYSTAF curveshows the tallest peak at 81.8° C. with a peak area of 34.7 percent aswell as a lower crystalline peak at 52.4° C. The separation between thetwo peaks is consistent with the presence of a high crystalline and alow crystalline polymer. The difference between the DSC Tm and theTcrystaf is 43.5° C.

Examples 5-19 Comparative Examples D*-F*, Continuous SolutionPolymerization, Catalyst A1/B2+DEZ

Continuous solution polymerizations are carried out in a computercontrolled autoclave reactor equipped with an internal stirrer. Purifiedmixed alkanes solvent (ISOPAR™ E available from ExxonMobil ChemicalCompany), ethylene at 2.70 lbs/hour (1.22 kg/hour), 1-octene, andhydrogen (where used) are supplied to a 3.8 L reactor equipped with ajacket for temperature control and an internal thermocouple. The solventfeed to the reactor is measured by a mass-flow controller. A variablespeed diaphragm pump controls the solvent flow rate and pressure to thereactor. At the discharge of the pump, a side stream is taken to provideflush flows for the catalyst and cocatalyst 1 injection lines and thereactor agitator. These flows are measured by Micro-Motion mass flowmeters and controlled by control valves or by the manual adjustment ofneedle valves. The remaining solvent is combined with 1-octene,ethylene, and hydrogen (where used) and fed to the reactor. A mass flowcontroller is used to deliver hydrogen to the reactor as needed. Thetemperature of the solvent/monomer solution is controlled by use of aheat exchanger before entering the reactor. This stream enters thebottom of the reactor. The catalyst component solutions are meteredusing pumps and mass flow meters and are combined with the catalystflush solvent and introduced into the bottom of the reactor. The reactoris run liquid-full at 500 psig (3.45 MPa) with vigorous stirring.Product is removed through exit lines at the top of the reactor. Allexit lines from the reactor are steam traced and insulated.Polymerization is stopped by the addition of a small amount of waterinto the exit line along with any stabilizers or other additives andpassing the mixture through a static mixer. The product stream is thenheated by passing through a heat exchanger before devolatilization. Thepolymer product is recovered by extrusion using a devolatilizingextruder and water cooled pelletizer. Process details and results arecontained in Table 2. Selected polymer properties are provided in Table3. TABLE 2 Process details for preparation of exemplary polymers Cat CatB2 DEZ Cocat Cocat Poly C₈H₁₆ Solv. H₂ A1² Cat A1 Flow B2³ Flow DEZ FlowConc. Flow [C₂H₄]/ Rate⁵ Conv Ex. kg/hr kg/hr sccm¹ T ° C. ppm kg/hr ppmkg/hr Conc % kg/hr ppm kg/hr [DEZ]⁴ kg/hr %⁶ Solids % Eff.⁷ D* 1.63 12.729.90 120 142.2 0.14 — — 0.19 0.32  820 0.17 536 1.81 88.8 11.2 95.2 E*″ 9.5 5.00 ″ — — 109 0.10 0.19 ″ 1743 0.40 485 1.47 89.9 11.3 126.8 F* ″11.3 251.6 ″ 71.7 0.06 30.8 0.06 — — ″ 0.11 — 1.55 88.5 10.3 257.7  5 ″″ — ″ ″ 0.14 30.8 0.13 0.17 0.43 ″ 0.26 419 1.64 89.6 11.1 118.3  6 ″ ″4.92 ″ ″ 0.10 30.4 0.08 0.17 0.32 ″ 0.18 570 1.65 89.3 11.1 172.7  7 ″ ″21.70 ″ ″ 0.07 30.8 0.06 0.17 0.25 ″ 0.13 718 1.60 89.2 10.6 244.1  8 ″″ 36.90 ″ ″ 0.06 ″ ″ ″ 0.10 ″ 0.12 1778 1.62 90.0 10.8 261.1  9 ″ ″78.43 ″ ″ ″ ″ ″ ″ 0.04 ″ ″ 4596 1.63 90.2 10.8 267.9 10 ″ ″ 0.00 12371.1 0.12 30.3 0.14 0.34 0.19 1743 0.08 415 1.67 90.31 11.1 131.1 11 ″ ″″ 120 71.1 0.16 ″ 0.17 0.80 0.15 1743 0.10 249 1.68 89.56 11.1 100.6 12″ ″ ″ 121 71.1 0.15 ″ 0.07 ″ 0.09 1743 0.07 396 1.70 90.02 11.3 137.0 13″ ″ ″ 122 71.1 0.12 ″ 0.06 ″ 0.05 1743 0.05 653 1.69 89.64 11.2 161.9 14″ ″ ″ 120 71.1 0.05 ″ 0.29 ″ 0.10 1743 0.10 395 1.41 89.42 9.3 114.1 152.45 ″ ″ ″ 71.1 0.14 ″ 0.17 ″ 0.14 1743 0.09 282 1.80 89.33 11.3 121.316 ″ ″ ″ 122 71.1 0.10 ″ 0.13 ″ 0.07 1743 0.07 485 1.78 90.11 11.2 159.717 ″ ″ ″ 121 71.1 0.10 ″ 0.14 ″ 0.08 1743 ″ 506 1.75 89.08 11.0 155.6 180.69 ″ ″ 121 71.1 ″ ″ 0.22 ″ 0.11 1743 0.10 331 1.25 89.93 8.8 90.2 190.32 ″ ″ 122 71.1 0.06 ″ ″ ″ 0.09 1743 0.08 367 1.16 90.74 8.4 106.0*Comparative, not an example of the invention¹standard cm³/min²[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl³bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconium dibenzyl⁴molar ratio in reactor⁵polymer production rate⁶percent ethylene conversion in reactor⁷efficiency, kg polymer/g M where g M = g Hf + g Zr

TABLE 3 Properties of exemplary polymers Heat of CRYSTAF Density Mw MnFusion T_(m) T_(c) T_(CRYSTAF) Tm − T_(CRYSTAF) Peak Area Ex. (g/cm³) I₂I₁₀ I₁₀/I₂ (g/mol) (g/mol) Mw/Mn (J/g) (° C.) (° C.) (° C.) (° C.)(percent) D* 0.8627 1.5 10.0 6.5 110,000 55,800 2.0 32 37 45 30 7 99 E*0.9378 7.0 39.0 5.6 65,000 33,300 2.0 183 124 113 79 45 95 F* 0.8895 0.912.5 13.4 137,300 9,980 13.8 90 125 111 78 47 20  5 0.8786 1.5 9.8 6.7104,600 53,200 2.0 55 120 101 48 72 60  6 0.8785 1.1 7.5 6.5 10960053300 2.1 55 115 94 44 71 63  7 0.8825 1.0 7.2 7.1 118,500 53,100 2.2 69121 103 49 72 29  8 0.8828 0.9 6.8 7.7 129,000 40,100 3.2 68 124 106 8043 13  9 0.8836 1.1 9.7 9.1 129600 28700 4.5 74 125 109 81 44 16 100.8784 1.2 7.5 6.5 113,100 58,200 1.9 54 116 92 41 75 52 11 0.8818 9.159.2 6.5 66,200 36,500 1.8 63 114 93 40 74 25 12 0.8700 2.1 13.2 6.4101,500 55,100 1.8 40 113 80 30 83 91 13 0.8718 0.7 4.4 6.5 132,10063,600 2.1 42 114 80 30 81 8 14 0.9116 2.6 15.6 6.0 81,900 43,600 1.9123 121 106 73 48 92 15 0.8719 6.0 41.6 6.9 79,900 40,100 2.0 33 114 9132 82 10 16 0.8758 0.5 3.4 7.1 148,500 74,900 2.0 43 117 96 48 69 65 170.8757 1.7 11.3 6.8 107,500 54,000 2.0 43 116 96 43 73 57 18 0.9192 4.124.9 6.1 72,000 37,900 1.9 136 120 106 70 50 94 19 0.9344 3.4 20.3 6.076,800 39,400 1.9 169 125 112 80 45 88

The resulting polymers are tested by DSC and ATREF as with previousexamples. Results are as follows:

The DSC curve for the polymer of Example 5 shows a peak with a 119.6° C.melting point (Tm) with a heat of fusion of 60.0 J/g. The correspondingCRYSTAF curve shows the tallest peak at 47.6° C. with a peak area of59.5 percent. The delta between the DSC Tm and the Tcrystaf is 72.0° C.

The DSC curve for the polymer of Example 6 shows a peak with a 115.2° C.melting point (Tm) with a heat of fusion of 60.4 J/g. The correspondingCRYSTAF curve shows the tallest peak at 44.2° C. with a peak area of62.7 percent. The delta between the DSC Tm and the Tcrystaf is 71.0° C.

The DSC curve for the polymer of Example 7 shows a peak with a 121.3° C.melting point with a heat of fusion of 69.1 J/g. The correspondingCRYSTAF curve shows the tallest peak at 49.2° C. with a peak area of29.4 percent. The delta between the DSC Tm and the Tcrystaf is 72.1° C.

The DSC curve for the polymer of Example 8 shows a peak with a 123.5° C.melting point (Tm) with a heat of fusion of 67.9 J/g. The correspondingCRYSTAF curve shows the tallest peak at 80.1° C. with a peak area of12.7 percent. The delta between the DSC Tm and the Tcrystaf is 43.4° C.

The DSC curve for the polymer of Example 9 shows a peak with a 124.6° C.melting point (Tm) with a heat of fusion of 73.5 J/g. The correspondingCRYSTAF curve shows the tallest peak at 80.8° C. with a peak area of16.0 percent. The delta between the DSC Tm and the Tcrystaf is 43.8° C.

The DSC curve for the polymer of Example 10 shows a peak with a 115.6°C. melting point (Tm) with a heat of fusion of 60.7 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 40.9° C. with apeak area of 52.4 percent. The delta between the DSC Tm and the Tcrystafis 74.7° C.

The DSC curve for the polymer of Example 11 shows a peak with a 113.6°C. melting point (Tm) with a heat of fusion of 70.4 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 39.6° C. with apeak area of 25.2 percent. The delta between the DSC Tm and the Tcrystafis 74.1° C.

The DSC curve for the polymer of Example 12 shows a peak with a 113.2°C. melting point (Tm) with a heat of fusion of 48.9 J/g. Thecorresponding CRYSTAF curve shows no peak equal to or above 30° C.(Tcrystaf for purposes of further calculation is therefore set at 30°C.). The delta between the DSC Tm and the Tcrystaf is 83.2° C.

The DSC curve for the polymer of Example 13 shows a peak with a 114.4°C. melting point (Tm) with a heat of fusion of 49.4 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 33.8° C. with apeak area of 7.7 percent. The delta between the DSC Tm and the Tcrystafis 84.4° C.

The DSC for the polymer of Example 14 shows a peak with a 120.8° C.melting point (Tm) with a heat of fusion of 127.9 J/g. The correspondingCRYSTAF curve shows the tallest peak at 72.9° C. with a peak area of92.2 percent. The delta between the DSC Tm and the Tcrystaf is 47.9° C.

The DSC curve for the polymer of Example 15 shows a peak with a 114.3°C. melting point (Tm) with a heat of fusion of 36.2 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 32.3° C. with apeak area of 9.8 percent. The delta between the DSC Tm and the Tcrystafis 82.0° C.

The DSC curve for the polymer of Example 16 shows a peak with a 116.6°C. melting point (Tm) with a heat of fusion of 44.9 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 48.0° C. with apeak area of 65.0 percent. The delta between the DSC Tm and the Tcrystafis 68.6° C.

The DSC curve for the polymer of Example 17 shows a peak with a 116.0°C. melting point (Tm) with a heat of fusion of 47.0 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 43.1° C. with apeak area of 56.8 percent. The delta between the DSC Tm and the Tcrystafis 72.9° C.

The DSC curve for the polymer of Example 18 shows a peak with a 120.5°C. melting point (Tm) with a heat of fusion of 141.8 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 70.0° C. with apeak area of 94.0 percent. The delta between the DSC Tm and the Tcrystafis 50.5° C.

The DSC curve for the polymer of Example 19 shows a peak with a 124.8°C. melting point (Tm) with a heat of fusion of 174.8 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 79.9° C. with apeak area of 87.9 percent. The delta between the DSC Tm and the Tcrystafis 45.0° C.

The DSC curve for the polymer of Comparative Example D* shows a peakwith a 37.3° C. melting point (Tm) with a heat of fusion of 31.6 J/g.The corresponding CRYSTAF curve shows no peak equal to and above 30° C.Both of these values are consistent with a resin that is low in density.The delta between the DSC Tm and the Tcrystaf is 7.3° C.

The DSC curve for the polymer of Comparative Example E* shows a peakwith a 124.0° C. melting point (Tm) with a heat of fusion of 179.3 J/g.The corresponding CRYSTAF curve shows the tallest peak at 79.3° C. witha peak area of 94.6 percent. Both of these values are consistent with aresin that is high in density. The delta between the DSC Tm and theTcrystaf is 44.6° C.

The DSC curve for the polymer of Comparative Example F* shows a peakwith a 124.8° C. melting point (Tm) with a heat of fusion of 90.4 J/g.The corresponding CRYSTAF curve shows the tallest peak at 77.6° C. witha peak area of 19.5 percent. The separation between the two peaks isconsistent with the presence of both a high crystalline and a lowcrystalline polymer. The delta between the DSC Tm and the Tcrystaf is47.2° C.

Physical Property Testing

Polymer samples are evaluated for physical properties such as hightemperature resistance properties, as evidenced by TMA temperaturetesting, pellet blocking strength, high temperature recovery, hightemperature compression set and storage modulus ratio, G′(25°C.)/G′(100° C.). Several commercially available polymers are included inthe tests: Comparative G* is a substantially linear ethylene/1-octenecopolymer (AFFINITY®, available from The Dow Chemical Company),Comparative H* is an elastomeric, substantially linear ethylene/1-octenecopolymer (AFFINITY®EG8100, available from The Dow Chemical Company),Comparative Example I* is a substantially linear ethylene/1-octenecopolymer (AFFINITY®PL1840, available from The Dow Chemical Company),Comparative Example J* is a hydrogenated styrene/butadiene/styrenetriblock copolymer (KRATON™ G1652, available from KRATON Polymers),Comparative Example K* is a thermoplastic vulcanizate (TPV, a polyolefinblend containing dispersed therein a crosslinked elastomer). Results arepresented in Table 4. TABLE 4 High Temperature Mechanical Properties300% Pellet Strain TMA-1 mm Blocking Recovery Compression penetrationStrength G′(25° C.)/ (80° C.) Set (70° C.) Ex. (° C.) lb/ft² (kPa)G′(100° C.) (percent) (percent) D* 51 — 9 Failed — E* 130 — 18 — — F* 70141 (6.8)  9 Failed 100  5 104 0 (0)  6 81 49  6 110 — 5 — 52  7 113 — 484 43  8 111 — 4 Failed 41  9 97 — 4 — 66 10 108 — 5 81 55 11 100 — 8 —68 12 88 — 8 — 79 13 95 — 6 84 71 14 125 — 7 — — 15 96 — 5 — 58 16 113 —4 — 42 17 108 0 (0)  4 82 47 18 125 — 10 — — 19 133 — 9 — — G* 75 463(22.2) 89 Failed 100 H* 70 213 (10.2) 29 Failed 100 I* 111 — 11 — — J*107 — 5 Failed 100 K* 152 — 3 — 40

In Table 4, Comparative Example F* (which is a physical blend of the twopolymers resulting from simultaneous polymerizations using catalyst A1and B1) has a 1 mm penetration temperature of about 70° C., whileExamples 5-9 have a 1 mm penetration temperature of 100° C. or greater.Further, examples 10-19 all have a 1 mm penetration temperature ofgreater than 85° C., with most having 1 mm TMA temperature of greaterthan 90° C. or even greater than 100° C. This shows that the novelpolymers have better dimensional stability at higher temperaturescompared to a physical blend. Comparative Example J* (a commercial SEBS)has a good 1 mm TMA temperature of about 107° C., but it has very poor(high temperature 70° C.) compression set of about 100 percent and italso failed to recover (sample broke) during a high temperature (80° C.)300 percent strain recovery. Thus the exemplified polymers have a uniquecombination of properties unavailable even in some commerciallyavailable, high performance thermoplastic elastomers.

Similarly, Table 4 shows a low (good) storage modulus ratio, G′(25°C.)/G′(100° C.), for the inventive polymers of 6 or less, whereas aphysical blend (Comparative Example F*) has a storage modulus ratio of 9and a random ethylene/octene copolymer (Comparative Example G*) ofsimilar density has a storage modulus ratio an order of magnitudegreater (89). It is desirable that the storage modulus ratio of apolymer be as close to 1 as possible. Such polymers will be relativelyunaffected by temperature, and fabricated articles made from suchpolymers can be usefully employed over a broad temperature range. Thisfeature of low storage modulus ratio and temperature independence isparticularly useful in elastomer applications such as in pressuresensitive adhesive formulations.

The data in Table 4 also demonstrate that the polymers of the inventionpossess improved pellet blocking strength. In particular, Example 5 hasa pellet blocking strength of 0 MPa, meaning it is free flowing underthe conditions tested, compared to Comparative Examples F* and G* whichshow considerable blocking. Blocking strength is important since bulkshipment of polymers having large blocking strengths can result inproduct clumping or sticking together upon storage or shipping,resulting in poor handling properties.

High temperature (70° C.) compression set for the inventive polymers isgenerally good, meaning generally less than about 80 percent, preferablyless than about 70 percent and especially less than about 60 percent. Incontrast, Comparative Examples F*, G*, H* and J* all have a 70° C.compression set of 100 percent (the maximum possible value, indicatingno recovery). Good high temperature compression set (low numericalvalues) is especially needed for applications such as gaskets, windowprofiles, o-rings, and the like. TABLE 5 Ambient Temperature MechanicalProperties Elon- Tensile 100% 300% Retractive Stress gation Abrasion:Notched Strain Strain Stress Relax- Flex Tensile Tensile at TensileElongation Volume Tear Recovery Recovery at 150% Compression ationModulus Modulus Strength Break¹ Strength at Break Loss Strength 21° C.21° C. Strain Set 21° C. at 50% Ex. (MPa) (MPa) (MPa)¹ (%) (MPa) (%)(mm³) (mJ) (percent) (percent) (kPa) (Percent) Strain² D* 12 5 — — 101074 — — 91 83 760 — — E* 895 589 — 31 1029 — — — — — — — F* 57 46 — —12 824 93 339 78 65 400 42 —  5 30 24 14 951 16 1116 48 — 87 74 790 1433  6 33 29 — — 14 938 — — — 75 861 13 —  7 44 37 15 846 14 854 39 — 8273 810 20 —  8 41 35 13 785 14 810 45 461 82 74 760 22 —  9 43 38 — — 12823 — — — — — 25 — 10 23 23 — — 14 902 — — 86 75 860 12 — 11 30 26 — —16 1090 — 976 89 66 510 14 30 12 20 17 12 961 13 931 — 1247  91 75 70017 — 13 16 14 — — 13 814 — 691 91 — — 21 — 14 212 160 — — 29 857 — — — —— — — 15 18 14 12 1127  10 1573 — 2074  89 83 770 14 — 16 23 20 — — 12968 — — 88 83 1040  13 — 17 20 18 — — 13 1252 — 1274  13 83 920  4 — 18323 239 — — 30 808 — — — — — — — 19 706 483 — — 36 871 — — — — — — — G*15 15 — — 17 1000 — 746 86 53 110 27 50 H* 16 15 — — 15 829 — 569 87 60380 23 — I* 210 147 — — 29 697 — — — — — — — J* — — — — 32 609 — — 93 961900  25 — K* — — — — — — — — — — — 30 —¹Tested at 51 cm/minute²measured at 38° C. for 12 hours

Table 5 shows results for mechanical properties for the new polymers aswell as for various comparison polymers at ambient temperatures. It maybe seen that the inventive polymers have very good abrasion resistancewhen tested according to ISO 4649, generally showing a volume loss ofless than about 90 mm³, preferably less than about 80 mm³, andespecially less than about 50 mm³. In this test, higher numbers indicatehigher volume loss and consequently lower abrasion resistance.

Tear strength as measured by tensile notched tear strength of theinventive polymers is generally 1000 mJ or higher, as shown in Table 5.Tear strength for the inventive polymers can be as high as 3000 mJ, oreven as high as 5000 mJ. Comparative polymers generally have tearstrengths no higher than 750 mJ.

Table 5 also shows that the polymers of the invention have betterretractive stress at 150 percent strain (demonstrated by higherretractive stress values) than some of the comparative samples.Comparative Examples F*, G* and H* have retractive stress value at 150percent strain of 400 kPa or less, while the inventive polymers haveretractive stress values at 150 percent strain of 500 kPa (Ex. 11) to ashigh as about 1100 kPa (Ex. 17). Polymers having higher than 150 percentretractive stress values would be quite useful for elastic applications,such as elastic fibers and fabrics, especially nonwoven fabrics. Otherapplications include diaper, hygiene, and medical garment waistbandapplications, such as tabs and elastic bands.

Table 5 also shows that stress relaxation (at 50 percent strain) is alsoimproved (less) for the inventive polymers as compared to, for example,Comparative Example G*. Lower stress relaxation means that the polymerretains its force better in applications such as diapers and othergarments where retention of elastic properties over long time periods atbody temperatures is desired.

Optical Testing TABLE 6 Polymer Optical Properties Ex. Internal Haze(percent) Clarity (percent) 45° Gloss (percent) F* 84 22 49 G* 5 73 56 5 13 72 60  6 33 69 53  7 28 57 59  8 20 65 62  9 61 38 49 10 15 73 6711 13 69 67 12 8 75 72 13 7 74 69 14 59 15 62 15 11 74 66 16 39 70 65 1729 73 66 18 61 22 60 19 74 11 52 G* 5 73 56 H* 12 76 59 I* 20 75 59

The optical properties reported in Table 6 are based on compressionmolded films substantially lacking in orientation. Optical properties ofthe polymers may be varied over wide ranges, due to variation incrystallite size, resulting from variation in the quantity of chainshuttling agent employed in the polymerization.

Extractions of Multi-Block Copolymers

Extraction studies of the polymers of Examples 5, 7 and ComparativeExample E* are conducted. In the experiments, the polymer sample isweighed into a glass fritted extraction thimble and fitted into aKumagawa type extractor. The extractor with sample is purged withnitrogen, and a 500 mL round bottom flask is charged with 350 mL ofdiethyl ether. The flask is then fitted to the extractor. The ether isheated while being stirred. Time is noted when the ether begins tocondense into the thimble, and the extraction is allowed to proceedunder nitrogen for 24 hours. At this time, heating is stopped and thesolution is allowed to cool. Any ether remaining in the extractor isreturned to the flask. The ether in the flask is evaporated under vacuumat ambient temperature, and the resulting solids are purged dry withnitrogen. Any residue is transferred to a weighed bottle usingsuccessive washes of hexane. The combined hexane washes are thenevaporated with another nitrogen purge, and the residue dried undervacuum overnight at 40° C. Any remaining ether in the extractor ispurged dry with nitrogen.

A second clean round bottom flask charged with 350 mL of hexane is thenconnected to the extractor. The hexane is heated to reflux with stirringand maintained at reflux for 24 hours after hexane is first noticedcondensing into the thimble. Heating is then stopped and the flask isallowed to cool. Any hexane remaining in the extractor is transferredback to the flask. The hexane is removed by evaporation under vacuum atambient temperature, and any residue remaining in the flask istransferred to a weighed bottle using successive hexane washes. Thehexane in the flask is evaporated by a nitrogen purge, and the residueis vacuum dried overnight at 40° C.

The polymer sample remaining in the thimble after the extractions istransferred from the thimble to a weighed bottle and vacuum driedovernight at 40° C. Results are contained in Table 7. TABLE 7 etherether C₈ hexane hexane C₈ residue wt. soluble soluble mole solublesoluble mole C₈ mole Sample (g) (g) (percent) percent¹ (g) (percent)percent¹ percent¹ Comp. F* 1.097 0.063 5.69 12.2 0.245 22.35 13.6 6.5Ex. 5 1.006 0.041 4.08 — 0.040 3.98 14.2 11.6 Ex. 7 1.092 0.017 1.5913.3 0.012 1.10 11.7 9.9¹Determined by ¹³C NMR

Additional Polymer Examples 19A-F, Continuous Solution Polymerization,Catalyst A1/B2+DEZ

Continuous solution polymerizations are carried out in a computercontrolled well-mixed reactor. Purified mixed alkanes solvent (ISOPAR™ Eavailable from ExxonMobil Chemical Company), ethylene, 1-octene, andhydrogen (where used) are combined and fed to a 27 gallon reactor. Thefeeds to the reactor are measured by mass-flow controllers. Thetemperature of the feed stream is controlled by use of a glycol cooledheat exchanger before entering the reactor. The catalyst componentsolutions are metered using pumps and mass flow meters. The reactor isrun liquid-full at approximately 550 psig pressure. Upon exiting thereactor, water and additive are injected in the polymer solution. Thewater hydrolyzes the catalysts, and terminates the polymerizationreactions. The post reactor solution is then heated in preparation for atwo-stage devolatization. The solvent and unreacted monomers are removedduring the devolatization process. The polymer melt is pumped to a diefor underwater pellet cutting.

Process details and results are contained in Table 8. Selected polymerproperties are provided in Table 9. TABLE 8 Polymerization Conditionsfor Polymers 19a-j. Cat Cat Cat A1² Cat A1 B2³ B2 DEZ DEZ C₂H₄ C₈H₁₆Solv. H₂ T Conc. Flow Conc. Flow Conc Flow Ex. lb/hr lb/hr lb/hr sccm¹ °C. ppm lb/hr ppm lb/hr wt % lb/hr 19a 55.29 32.03 323.03 101 120 6000.25 200 0.42 3.0 0.70 19b 53.95 28.96 325.3 577 120 600 0.25 200 0.553.0 0.24 19c 55.53 30.97 324.37 550 120 600 0.216 200 0.609 3.0 0.69 19d54.83 30.58 326.33 60 120 600 0.22 200 0.63 3.0 1.39 19e 54.95 31.73326.75 251 120 600 0.21 200 0.61 3.0 1.04 19f 50.43 34.80 330.33 124 120600 0.20 200 0.60 3.0 0.74 19g 50.25 33.08 325.61 188 120 600 0.19 2000.59 3.0 0.54 19h 50.15 34.87 318.17 58 120 600 0.21 200 0.66 3.0 0.7019i 55.02 34.02 323.59 53 120 600 0.44 200 0.74 3.0 1.72 19j 7.46 9.0450.6 47 120 150 0.22 76.7 0.36 0.5 0.19 [Zn]⁴ Cocat 1 Cocat 1 Cocat 2Cocat 2 in Poly Conc. Flow Conc. Flow polymer Rate⁵ Conv⁶ Ex. ppm lb/hrppm lb/hr ppm lb/hr wt % Polymer wt % Eff.⁷ 19a 4500 0.65 525 0.33 24883.94 88.0 17.28 297 19b 4500 0.63 525 0.11  90 80.72 88.1 17.2 295 19c4500 0.61 525 0.33 246 84.13 88.9 17.16 293 19d 4500 0.66 525 0.66 49182.56 88.1 17.07 280 19e 4500 0.64 525 0.49 368 84.11 88.4 17.43 288 19f4500 0.52 525 0.35 257 85.31 87.5 17.09 319 19g 4500 0.51 525 0.16 19483.72 87.5 17.34 333 19h 4500 0.52 525 0.70 259 83.21 88.0 17.46 312 19i4500 0.70 525 1.65 600 86.63 88.0 17.6 275 19j — — — — — — — — —¹standard cm³/min²[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl³bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconium dimethyl⁴ppm in final product calculated by mass balance⁵polymer production rate⁶weight percent ethylene conversion in reactor⁷efficiency, kg polymer/g M where g M = g Hf + g Z

TABLE 9 Polymer Physical properties Heat of CRYSTAF Polymer Ex. DensityMw Mn Fusion Tm TCRYSTAF Tm − TCRYSTAF Peak Area No. (g/cc) I2 I10I10/I2 (g/mol) (g/mol) Mw/Mn (J/g) (° C.) Tc (° C.) (° C.) (° C.) (wt %)19g 0.8649 0.9 6.4 7.1 135000 64800 2.1 26 120 92 30 90 90 19h 0.86541.0 7.0 7.1 131600 66900 2.0 26 118 88 — — —

TABLE 9A Average Block Index For exemplary polymers¹ Example Zn/C₂ ²Average BI Polymer f 0 0 Polymer 8 0.56 0.59 Polymer 19a 1.3 0.62Polymer 5 2.4 0.52 Polymer 19b 0.56 0.54 Polymer 19h 3.15 0.59¹Additional information regarding the calculation of the block indicesfor various polymers is disclosed in U.S. Patent Application Serial No.     (insert when known), entitled “Ethylene/α-Olefin BlockInterpolymers”, filed on Mar. 15, 2006, in the name of Colin L. P. Shan,Lonnie Hazlitt, et. al. and assigned to Dow Global Technologies Inc.,the disclose which is incorporated by reference herein in its entirety.²Zn/C₂ * 1000 = (Zn feed flow * Zn concentration/1000000/Mw ofZn)/(Total Ethylene feed flow * (1 − fractional ethylene conversionrate)/Mw of Ethylene) * 1000. Please note that “Zn” in “Zn/C₂ * 1000”refers to the amount of zinc in diethyl zinc (“DEZ”) used in thepolymerization process, and “C2” refers to the amount of ethylene usedin the polymerization process.

Comparative Examples L-P

Comparative Example L was a f-PVC, i.e., flexible poly(vinyl chloride),(obtained from Wofoo Plastics, Hong Kong, China). Comparative Example Mwas a SBS copolymer, VECTOR™ 7400 (obtained from Dexco Polymers,Houston, Tex.). Comparative Example N was a partially crosslinked TPV,VYRAM™ TPV 9271-65 (obtained from Advanced Elastomer Systems, Akron,Ohio). Comparative Example 0 was a SEBS copolymer, KRATON® G2705(obtained from Kraton Polymers, Houston, Tex.). Comparative Example Pwas a SBS copolymer, KRATON® G3202 (obtained from Kraton Polymers,Houston, Tex.).

Examples 20-26

Example 20 was 100% of Example 19f. Example 21 was similar to Example20, except that 30% of Example 19f was replaced with a high densitypolyethylene (HDPE), DMDA-8007 (from The Dow Chemical Company, Midland,Mich.). Example 22 was similar to Example 20, except that 20% of Example19f was replaced with DMDA-8007. Example 23 was similar to Example 20,except that 10% of Example 19f was replaced with DMDA-8007. Example 24was similar to Example 20, except that 30% of Example 19f was replacedwith a homopolymer polypropylene, H700-12 (from The Dow ChemicalCompany, Midland, Mich.). Example 25 was similar to Example 20, exceptthat 20% of Example 19f was replaced with H700-12. Example 26 wassimilar to Example 20, except that 10% of Example 19f was replaced withH700-12.

Comparative Examples Q-X

Comparative Example Q was similar to Example 21, except that Example 19fwas replaced with a polyolefin elastomer, ENGAGE® ENR 7380 (from DuPontDow Elastomers, Wilmington, Del.). Comparative Example R was similar toExample 24, except that Example 19f was replaced with ENGAGE® ENR 7380.Comparative Example S was similar to Example 20, except that Example 19fwas replaced with a polyolefin elastomer, ENGAGE® 8407 (from DuPont DowElastomers, Wilmington, Del.) and the sample is 30 mil (0.762 mm) thick.Comparative Example T was similar to Example 20, except that Example 19fwas replaced with a polyolefin elastomer, ENGAGE® 8967 (from DuPont DowElastomers, Wilmington, Del.). Comparative Example U was similar toExample 24, except that Example 19f was replaced with apropylene-ethylene copolymers, VERSIFY® DE3300 (from The Dow ChemicalCompany, Midland, Mich.). Comparative Example V was similar to Example24, except that Example 19f was replaced with a propylene-ethylenecopolymer, VERSIFY® DE3400 (from The Dow Chemical Company, Midland,Mich.). Comparative Example W was similar to Example 22, except thatExample 19f was replaced with VERSIFY® DE3300. Comparative Example X wassimilar to Example 322 except that Example 19f was replaced withVERSIFY® DE3400.

Examples 27-33

Example 27 was a mixture of 56% of Example 19f, 16% of H700-12, and 28%of RENOIL® 625 (an oil from Renkert Oil Elversony, Pa.). Example 28 wassimilar to Example 27, except that the mixture was 33% of Example 19f,17% of H700-12, and 50% of RENOIL® 625. Example 29 was similar toExample 27, except that the mixture was 56% of Example 19f, 16% ofDMDA-8007, and 28% of RENOIL® 625. Example 30 was similar to Example 27,except that the mixture was 33% of Example 19f, 17% of DMDA-8007, and50% of RENOIL® 625. Example 31 was similar to Example 27, except thatthe mixture was 17% of Example 19f, 16% of H700-12, 16% of KRATON® G2705and 50% of RENOIL® 625. Example 32 was similar to Example 20, exceptthat 1% of AMPACET® 10090 (an Erucamide concentrate from AmpacetCorporation, Tarrytown, N.Y.), was added as the slip/anti-blockingagent. Example 33 was similar to Example 32, except that 5% of AMPACET®10090 was added as the slip/anti-blocking agent.

Mechanical and Physical Properties Measurements

The Thermomechanical (TMA) properties, hardness, compression setproperties, flexural modulus, gull wing tear strength, Vicat softeningpoint, blocking property, scratch mar resistance, ultimate elongation,100% modulus, 300% modulus, ultimate tensile strength, and yieldstrength of Comparative Examples L-X and Examples 20-33 were measuredand the results are shown in Tables 10 and 11 below.

The penetration temperature by thermal mechanical analysis (TMA)technique was conducted on 30 mm diameter×3.3 mm thick, compressionmolded discs, formed at 180° C. and 10 MPa molding pressure for 5minutes and then air quenched. The instrument used was a Perkin-ElmerTMA 7. In the TMA test, a probe with 1.5 mm radius tip (P/N N519-0416)was applied to the surface of the sample disc with 1N force. Thetemperature was raised at 5° C./minute from 25° C. The probe penetrationdistance was measured as a function of temperature. The experiment endedwhen the probe had penetrated 0.1 mm and 1 mm respectively into thesample. The 0.1 mm and 1 mm penetration temperatures of each example arelisted in Table 10 below.

The Shore D hardness of each sample was measured according to ASTM D2240, which is incorporated herein by reference.

The compression set properties of each sample at 23° C. and 70° C. weremeasured according to ASTM D 4703, which is incorporated herein byreference.

The flexural modulus of each sample was measured according to the methoddescribed in ASTM D 790, which is incorporated herein by reference.

The gull wing tear strength of each sample was measured according to themethod described in ASTM D 1004, which is incorporated herein byreference.

The Vicat softening point of each sample was measured according to themethod described in ASTM D1525, which is incorporated herein byreference.

The blocking of each sample was measured by stacking six each4″×4′×0.125″ injection molded plaques, leaving the plaques at ambientconditions (73 F) for 24 hours, then un-stacking the plaques. Theblocking rating is between 1 and 5 with 5 being excellent (all theplaques easily un-stacked) to 1 being unacceptable (where the 6 plaqueshad adhered to each other so much that none of the plaques could beseparated by hand).

The scratch mar resistance of each sample was measured by manuallyscribing a X on a 4×4×0.125 inch plaque from corner to corner with arounded plastic stylus. The scratch mar resistance rating is between 1and 5 with 5 is excellent (where no evidence of the X is visible) and 1is unacceptable (where the X is highly visible and can not be rubbedoff).

The 100% modulus, 300% modulus, ultimate tensile strength, ultimateelongation, and yield strength of each sample were measured according toASTM D 412, which is incorporated herein by reference. TABLE 10 0.1 mm1.0 mm Compression Compression Flexural Tear Vicat TMA TMA Set at Set atModulus Strength Softening Scratch Mar Sample (° C.) (° C.) Shore D 70°C. 23° C. (psi) (lbs/in) Point (° C.) Blocking Resistance Comp. Ex. L 49129 53 67 49 26654 391 69 5 4 Comp. Ex. M 25 78 10 91 17 1525 / 58 5 4Comp. Ex. N 60 146 15 51 30 4613 149 65 4 4 Comp. Ex. O 71 137 / 40 212781 169 / 3 1 Comp. Ex. P 53 71 / 106  15 2043 149 / 1 1 Example 20 6799 17 57 21 4256 206 44 1 1 Example 21 94 111 34 55 43 22071 441 66 1 1Example 22 98 113 33 56 31 14261 323 59 1 1 Example 23 74 103 25 52 286943 254 50 1 1 Example 24 99 111 36 66 37 24667 421 67 1 1 Example 2584 104 30 61 29 12325 331 55 1 1 Example 26 81 104 24 61 23 / 257 47 1 1Comp. Ex. Q 101 119 41 63 10 21358 426 59 1 1 Comp. Ex. R 101 146 41 9727 20267 / 58 3 3 Comp. Ex. S 35 52 16 112  35 2116 186 / 1 1 Comp. Ex.T 48 95 22 83 37 6475 234 / 2 1 Comp. Ex. U 116 142 40 / / / / / 3 4Comp. Ex. V 53 113 33 / / 21348 / / 1 3 Comp. Ex. W 68 95 33 76 44 11497328 / 2 3 Comp. Ex. X 40 64 25 87 40 11384 281 / 1 1 Example 27 76 10518 48 28 / 252 / 2 1 Example 28 49 95 13 57 27 / 177 / 2 2 Example 29 63106 18 42 30 / 215 47 2 1 Example 30 54 99 10 / / / / 48 2 2 Example 3148 99 12 55 41 / / 57 3 2 Example 32 69 99 20 54 21 / / 44 5 4 Example33 74 99 19 52 19 / / 44 5 5

TABLE 11 Ultimate 100% 300% Tensile Ultimate Yield Modulus ModulusStrength Elongation Strength Sample (psi) (psi) (psi) (%) (psi) Comp.Ex. L 1934 0 2522 224 607 Comp. Ex. M 198 140 549 505 45 Comp. Ex. N 336175 604 459 122 Comp. Ex. O 213 118 1038 656 82 Comp. Ex. P 613 0 563 97253 Example 20 333 130 672 1039 162 Example 21 795 258 1430 1007 652Example 22 589 198 1062 1026 443

Comparative Examples L, M, N, O and P are commercial flexible moldedgoods resins which are not olefin-based. Examples 20-26 are variousembodiments of this invention (as a base resin or as a blend of the baseresin with PP and/or HDPE) demonstrating the improved balance of lowmodulus and high upper service temperature. Comparative Examples Q-X arecommercial flexible molded good resins that are olefin-based. Examples20-26 demonstrate the improved balance of low modulus and high upperservice temperature over Comparative Examples Q-X.

SEBS/Inventive Interpolymer Blends

Blends of ethylene/α-olefin block copolymer and hydrogenated styrenicsblock copolymer (OBC/SEBS) were prepared using a Haake Rheomix 300rheometer. The temperature of the sample bowl was set at 190° C. and therotor speed was 40 rpm. After all the components were added, the mixingwas continued for about five minutes or until a stable torque has beenestablished. Samples for further testing and evaluation were compressionmolded a Garver automatic press at 190° C. under 44.45 kN force for 3minutes. The molten materials were subsequently quenched with the pressequilibrated at room temperature using an electronic cooling bath.

Comparative Examples Y1-Y5

Comparative Example Y1 was 100% of KRATON® G1652, astyrene-ethylene/butylenes-styrene block copolymer available from ShellChemical Company, Houston, Tex. Comparative Example Y1 was the same asComparative Example J*. Comparative Example Y2 was a blend of 75% ofKRATON® G1652 and 25% of AFFINITY® EG8100. Comparative Example Y3 was ablend of 50% of KRATON® G1652 and 50% of AFFINITY® EG8100. ComparativeExample Y4 was a blend of 25% of KRATON®G1652 and 75% of AFFINITY®EG8100. Comparative Example Y5 was 100% AFFINITY® EG8100. ComparativeExample Y5 was the same as Comparative Example H*.

Examples 34-45

Example 34 was a blend of 75% of KRATON® G1652 and 25% of Example orPolymer 19a. Example 35 was a blend of 50% of KRATON® G1652 and 50% ofExample 19a. Example 36 was a blend of 25% of KRATON® G1652 and 75% ofExample 19a. Example 37 was the same as Example 19a. Example 38 was ablend of 75% of KRATON® G1652 and 25% of Example 19b. Example 39 was ablend of 50% of KRATON® G1652 and 50% of Example 19b. Example 40 was ablend of 25% of KRATON® G1652 and 75% of Example 19b. Example 41 was thesame as Example 19b. Example 42 was a blend of 75% of KRATON® G1652 and25% of Polymer 19i. Polymer 19i was an interpolymer preparedsubstantially similarly to Examples 1-19 and Example 19a-19h. Oneskilled in the art knows how to manipulate process conditions, such asshuttling agent ratios, hydrogen flow, monomer concentration, etc., tomake a target polymer using the process conditions already detailed inthe instant application. Example 43 was a blend of 50% of KRATON® G1652and 50% of Polymer 19i. Example 44 was a blend of 25% of KRATON® G1652and 75% of Polymer 19i. Example 45 was 100% of Polymer 19i.

Mechanical and Physical Properties Measurement

The thermomechanical (TMA) properties, elastic recovery at 300% strain,elongation at break, tensile strength and elmendorf tear strength ofcomparative examples Y1-Y5 and Examples 34-45 were measured by methodsdescribed herein and known to one of skill in the art and the resultsare shown in Table 12 below. TABLE 12 Compositions and properties ofSEBS blends of Examples 34-45 and Comparative Examples Y1-Y5. TMAElastic Elongation Tensile Component Temperature Recovery @ BreakStrength Elmendorf B content, % Component B² (° C.)¹ @300% strain (%)(MPa) tear (g/mil) Comparative Example Y1 0 AFFINITY ® EG8100³ 97 92589.8 21.2 70.2 Comparative Example Y2 25 AFFINITY ® EG8100 86 90 675.823.82 81.04 Comparative Example Y3 50 AFFINITY ® EG8100 71 82 664.317.08 47.57 Comparative Example Y4 75 AFFINITY ® EG8100 63.3 73 746.517.44 43.16 Comparative Example Y5 100 AFFINITY ® EG8100 60.2 61.7 777.413.52 55.6 Example 34 25 19a⁴ 100 92 742.4 28.46 50.71 Example 35 50 19a103 89 763.3 18.75 51.02 Example 36 75 19a 106 83.7 827.9 17.77 56.89Example 37 100 19a 107.2 78.3 986.4 13.63 204.3 Example 38 25 19b⁵ 99.592.7 693.6 24.45 41.27 Example 39 50 19b 101 90 770.8 21.1 36.05 Example40 75 19b 104.9 86 813.1 18.18 34.7 Example 41 100 19b 106 80 931.513.93 67.76 Example 42 25 19i⁶ 100 93.3 672 22.13 47.11 Example 43 5019i 102.5 91 704.1 15.62 34.76 Example 44 75 19i 103.7 88 1059 18.4220.85 Example 45 100 19i 108 80.2 1518 13.3 39.5Notes:¹TMA temperature was measured at 1 mm penetration with a heating rate of5° C./min under 1N force.²The rest is Component A which is KRATON ® G1652, a SEBS available fromShell Chemical Company.³AFFINITY ® EG8100 is a substantially linear ethylene/1-octene copolymerhaving I₂ of 1 g/10 min. (ASTM D-1238) and density of 0.870 g/cc(ASTMD-792).⁴19a is an inventive ethylene/octene copolymer having I₂ of 1 g/10 min.and density of 0.878 g/cc.⁵19b is an inventive ethylene/octene copolymer having I₂ of 1 g/10 min.and density of 0.875 g/cc.⁶19i is an inventive ethylene/butene copolymer having I₂ of 1 g/10 min.and density of 0.876 g/cc.

Elastic recovery properties of exemplary blends (i.e., Examples 34-45)and Comparative Examples Y1-Y5 at various amounts of SEBS (i.e., KRATON®G1652) in the blend are shown in FIG. 8. The TMA temperatures ofexemplary blends and Comparative Examples 1-5 at various amounts of SEBSin the blend are shown in FIG. 9. As seen in Table 12 and FIGS. 8-9, theexemplary blends (i.e., Examples 34-45) exhibit improved heat resistanceand elastic recovery properties over the corresponding ComparativeExamples Y1-Y5.

HMS-HDPE/Inventive Interpolymer or HMS-PP/INvebtive Interpolymer BlendsComparative Examples Z1-Z4

Comparative Example Z1 was 100% of Polymer 19j. Polymer 19j was aninventive ethylene/octene copolymer having a Zn level of 517 ppm, adensity of 0.877 g/cc and a melt index (I₂) of 5. Comparative Example Z2was 100% of Polymer 19k. Polymer 19k was an inventive ethylene/octenecopolymer having a Zn level of 693 ppm, a density of 0.877 g/cc and amelt index (I₂) of 5. Comparative Example Z3 was 100% of Polymer 19l.Polymer 19l was an inventive ethylene/octene copolymer having a densityof 0.877 g/cc and a melt index (I₂) of 30. Comparative Example Z4 was100% of Polymer 19m. Polymer 19m was an inventive ethylene/octenecopolymer having a Zn level of 255 ppm, a density of 0.866 g/cc and amelt index (I₂) of 5. Polymers 19j, 19k, 19l and 19m were preparedsubstantially similarly to Examples 1-19 and Example 19a-19h. Oneskilled in the art knows how to manipulate process conditions, such asshuttling agent ratios, hydrogen flow, monomer concentration, etc., tomake a target polymer using the process conditions already detailed inthe instant application.

Examples 46-57

Example 46 was a blend of 90% of Polymer 19m and 10% of PROFAX® PF814, aHMS-PP from Basell Polyolefins, Elkton, Md. Example 47 was a blend of85% of Polymer 19m and 15% of PROFAX® PF814. Example 48 was a blend of95% of Polymer 19m and 5% of PROFAX® PF814. Example 49 was a blend of95% of Polymer 19j and 5% of PROFAX® PF814. Example 50 was a blend of90% of Polymer 19j and 10% of PROFAX® PF814. Example 51 was a blend of85% of Polymer 19j and 15% of PROFAX® PF814. Example 52 was a blend of85% of Polymer 19k and 15% of PROFAX® PF814. Example 53 was a blend of90% of Polymer 19k and 10% of PROFAX® PF814. Example 54 was a blend of95% of Polymer 19k and 5% of PROFAX® PF814. Example 55 was a blend of95% of Polymer 19l and 5% of PROFAX® PF814. Example 56 was a blend of90% of Polymer 19l and 10% of PROFAX® PF814. Example 57 was a blend of85% of Polymer 19l and 15% of PROFAX® PF814.

Comparative Examples Z1-Z4 and Examples 46-57 were dry blended (if ablend) and then injection molded using a 80 ton Arburg 370C injectionmolding machine (available from ARBURG GmbH+Co KG, Lossburg, Germany)into a 4 inch by 6 inch by 0.125 inch test plaque. The mold had apolished smooth surface and used a cold runner through a fan gate. Themolding conditions were held constant at 23 seconds total cycle time (totest the ability of the resins to solidify quickly).

Comparative Examples Z1-Z4 and Examples 46-57 were injection molded asdescribed above into plaques or parts, which were subsequently sujbectedto “Parts Stick in Mold” test, “Parts Initially Stick Together” test,Shore A hardness, “Part Quality” test and “Aged Part Tackiness” test.

The “Parts Stick in Mold” test included observing whether the moldedparts adhered to the mold surfaces and would not be ejected from themold. A “Yes” rating is unfavorable and means that the molded parts didstick in the mold and required manual extraction. A “No” is favorableand means that the molded parts did not stick in the mold and fell tothe conveyor system without manual extraction. In the “Parts InitiallyStick Together” test, two molded parts of each sample immediately afterinjection molding were placed on top of each other; hand pressure wasapplied; and then the molded parts were pulled away from each other. Theamount of force required to remove the two parts from each other wasmeasured. A rating for each pair was given from 3 (best, no sticking, noforce required to remove the two samples) to 1 (worse, excessivesticking, substantial hand force was required to removed the twosamples). The molded parts were then set aside and laid flat for 24hours. After 24 hours, the Shore A hardness of each molded part wasmeasured according to ASTM D2240, which is incorporated herein byreference. The average of two Shore A hardness readings for each samplewere recorded. Further, each molded part was graded for “Part Quality”and “Aged Part Tackiness.” The “Part Quality” was rated from 5 (best,absolute perfect part without voids, warpage, shrinkage) to 1 (worse,excessive voids, a warped parts, excessive shrinkage). The “Aged PartTackiness” was tested by placing two molded parts on top of each other;applying hand pressure, and pulling the parts away from each other. Theamount of force required to remove the two parts from each other wasmeasured. A rating of each pair was given from 5 (best, no sticking, noforce required to remove the two samples) to 1 (worse, excessivesticking, substantial hand force was required to removed the twosamples). The test results of Comparative Examples Z1-Z4 and Examples46-57 are shown in Table 13 below. TABLE 13 Tacky Flexible ModifyingParts Resin Resin Part sticks initially stick Shore A Part Aged PartSample Component Component in mold together¹ Hardness Quality²Tackiness³ Comparative 100% NONE yes 1 74 3 1 Example Z1 Polymer 19jComparative 100% NONE yes 1 76 3 1 Example Z2 Polymer 19k Comparative100% NONE yes 1 71 4 1 Example Z3 Polymer 19l Comparative 100% NONE yes1 63 4 1 Example Z4 Polymer 19m Example 46  90% 10% no 3 76 5 5 Polymer19m PROFAX ® PF814 Example 47  85% 15% no 3 77 5 5 Polymer 19m PROFAX ®PF814 Example 48  95%  5% no 2 66 4 4 Polymer 19m PROFAX ® PF814 Example49  95%  5% no 2 80 5 4 Polymer 19j PROFAX ® PF814 Example 50  90% 10%no 3 81 5 5 Polymer 19j PROFAX ® PF814 Example 51  85% 15% no 3 86 5 5Polymer 19j PROFAX ® PF814 Example 52  85% 15% no 3 84 5 5 Polymer 19kPROFAX ® PF814 Example 53  90% 10% no 3 84 5 5 Polymer 19k PROFAX ®PF814 Example 54  95%  5% no 2 80 5 4 Polymer 19k PROFAX ® PF814 Example55  95%  5% no 2 80 5 4 Polymer 19k PROFAX ® PF814 Example 56  90% 10%no 3 83 5 5 Polymer 19k PROFAX ® PF814 Example 57  85% 15% no 3 87 5 5Polymer 19k PROFAX ® PF814Note:¹The scale of the “Parts initially stick together” test is 3 = best 1 =worst;²the scale of the “Part Quality” test is 5 = best (no tackiness), 1 =worse (extreme tackiness);³the scale of the “Aged Part Tackiness” is 5 = best (minimal shrink, nobubbles, no curl, flat part), 1 = worse (excessive shrink, bubbles,curled part).

The test data in Table 13 indicate that the tackiness and hardness ofthe inventive the ethylene/α-olefin interpolymers (e.g., Polymers 19j,19k, 19l, and 19m) can be improved by blending each of them with aHMS-PP such as PROFAX® PF814.

Some of the polymer blends disclosed herein can provide a bettercombination of moldability, appealing appearance, non-stickiness andmechanical properties than any of the components of the polymer blendsalone. For example, Examples 21-26, which are polymer blends of Polymer19f and at least one other polymer, demonstrate a better balance offlexural modulus, tear strength, and 0.1 mm pentration temperature byTMA than those of Polymer 19f alone (i.e., Example 20) or ComparativeExamples M-P, which are not polymer blends. Similarly, the polymerblends comprising Polymer 19a, 19b or 19i (i.e, Examples 34-36, 38-40and 42-44) has a better balance of 1 mm pentration temperature by TMAand elastic recovery than KRATON® G1652, AFFINITY® EG8100 or thecorresponding Polymer 19a, 19b or 19i alone. Similarly, the polymerblends comprising Polymer 19j, 19k, 19l or 19m (i.e, Examples 46-57) hasa better balance of tackiness (i.e., lower tackiness) and hardness (i.e,higher hardness) than the corresponding Polymer 19j, 19k, 19l or 19malone.

As demonstrated above, embodiments of the invention provide variouspolymer blends which possess unique physical and mechanical propertiesthat are suitable for making molded articles for a variety ofapplications. The blends have relatively low modulus, while maintainingrelatively high heat resistance. Such balance of properties makes theblends suitable for making flexible molded articles. Moreover, someblends exhibit little or no stickiness in the surface.

While the invention has been described with respect to a limited numberof embodiments, the specific features of one embodiment should not beattributed to other embodiments of the invention. No single embodimentis representative of all aspects of the invention. In some embodiments,the compositions or methods may include numerous compounds or steps notmentioned herein. In other embodiments, the compositions or methods donot include, or are substantially free of, any compounds or steps notenumerated herein. Variations and modifications from the describedembodiments exist. Finally, any number disclosed herein should beconstrued to mean approximate, regardless of whether the word “about” or“approximately” is used in describing the number. The appended claimsintend to cover all those modifications and variations as falling withinthe scope of the invention.

1. A polymer blend comprising: (i) at least one ethylene/α-olefininterpolymer, wherein the ethylene/α-olefin interpolymer: (a) has aMw/Mn from about 1.7 to about 3.5, at least one melting point, Tm, indegrees Celsius, and a density, d, in grams/cubic centimeter, whereinthe numerical values of Tm and d correspond to the relationship:T _(m)≧2002.9+4538.5(d)−2422.2(d)₂; or (b) has a Mw/Mn from about 1.7 toabout 3.5, and is characterized by a heat of fusion, ΔH in J/g, and adelta quantity, ΔT, in degrees Celsius defined as the temperaturedifference between the tallest DSC peak and the tallest CRYSTAF peak,wherein the numerical values of ΔT and ΔH have the followingrelationships:ΔT≧−0.1299(ΔH)+62.81 for ΔH greater than zero and up to 130 J/g,ΔT≧48° C. for ΔH greater than 130 J/g,  wherein the CRYSTAF peak isdetermined using at least 5 percent of the cumulative polymer, and ifless than 5 percent of the polymer has an identifiable CRYSTAF peak,then the CRYSTAF temperature is 30° C.; or (c) is characterized by anelastic recovery, Re, in percent at 300 percent strain and 1 cyclemeasured with a compression-molded film of the ethylene/α-olefininterpolymer, and has a density, d, in grams/cubic centimeter, whereinthe numerical values of Re and d satisfy the following relationship whenthe ethylene/α-olefin interpolymer is substantially free of across-linked phase:Re>1481−1629(d); or (d) has a molecular fraction which elutes between40° C. and 130° C. when fractionated using TREF, characterized in thatthe fraction has a molar comonomer content of at least 5 percent higherthan that of a comparable random ethylene interpolymer fraction elutingbetween the same temperatures, wherein said comparable random ethyleneinterpolymer has the same comonomer(s) and has a melt index, density,and molar comonomer content (based on the whole polymer) within 10percent of that of the ethylene/α-olefin interpolymer; or (e) ischaracterized by a storage modulus at 25° C., G′(25° C.), and a storagemodulus at 100° C., G′(100° C.), wherein the ratio of G′(25° C.) toG′(100° C.) is from about 1:1 to about 10:1; and (ii) at least onepolyolefin, or at least one styrenic block copolymer, or a combinationthereof.
 2. The polymer blend of claim 1, wherein the ethylene/α-olefininterpolymer has a Mw/Mn from about 1.7 to about 3.5, at least onemelting point, Tm, in degrees Celsius, and a density, d, in grams/cubiccentimeter, wherein the numerical values of Tm and d correspond to therelationship:Tm≧858.91−1825.3(d)+1112.8(d)².
 3. The polymer blend of claim 1, whereinthe ethylene/α-olefin interpolymer has a Mw/Mn from about 1.7 to about3.5 and is characterized by a heat of fusion, ΔH in J/g, and a deltaquantity, ΔT, in degrees Celsius defined as the temperature differencebetween the tallest DSC peak and the tallest CRYSTAF peak, wherein thenumerical values of ΔT and ΔH have the following relationships:ΔT>−0.1299(ΔH)+62.81 for ΔH greater than zero and up to 130 J/g,ΔT>48° C. for ΔH greater than 130 J/g, wherein the CRYSTAF peak isdetermined using at least 5 percent of the cumulative polymer, and ifless than 5 percent of the polymer has an identifiable CRYSTAF peak,then the CRYSTAF temperature is 30° C.
 4. The polymer blend of claim 1,wherein the ethylene/α-olefin interpolymer is characterized by anelastic recovery, Re, in percent at 300 percent strain and 1 cyclemeasured with a compression-molded film of the ethylene/α-olefininterpolymer, and has a density, d, in grams/cubic centimeter, whereinthe numerical values of Re and d satisfy the following relationship whenthe ethylene/α-olefin interpolymer is substantially free of across-linked phase:Re>1481−1629(d).
 5. The polymer blend of claim 4, wherein the numericalvalues of Re and d satisfy the following relationship:Re>1491−1629(d).
 6. The polymer blend of claim 4, wherein the numericalvalues of Re and d satisfy the following relationship:Re>1501−1629(d).
 7. The polymer blend of claim 4, wherein the numericalvalues of Re and d satisfy the following relationship:Re>1511−1629(d).
 8. The polymer blend of claim 1, wherein theethylene/α-olefin interpolymer has a molecular fraction which elutesbetween 40° C. and 130° C. when fractionated using TREF, characterizedin that the fraction has a molar comonomer content of at least 5 percenthigher than that of a comparable random ethylene interpolymer fractioneluting between the same temperatures, wherein said comparable randomethylene interpolymer has the same comonomer(s) and has a melt index,density, and molar comonomer content (based on the whole polymer) within10 percent of that of the ethylene/α-olefin interpolymer.
 9. The polymerblend of claim 1, wherein the ethylene/α-olefin interpolymer ischaracterized by a storage modulus at 25° C., G′(25° C.), and a storagemodulus at 100° C., G′(100° C.), wherein the ratio of G′(25° C.) toG′(100° C.) is from about 1:1 to about 10:1.
 10. The polymer blend ofclaim 1, wherein the α-olefin in the ethylene/α-olefin interpolymer isstyrene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene,norbornene, 1-decene, 1,5-hexadiene, or a combination thereof.
 11. Thepolymer blend of claim 1, wherein the ethylene/α-olefin interpolymer ispresent in the range from about 5% to about 95% by weight of the totalcomposition.
 12. The polymer blend of claim 1, wherein the polyolefin isan olefin homopolymer, an olefin copolymer, an olefin terpolymer or acombination thereof.
 13. The polymer blend of claim 1, wherein thepolyolefin is a high melt strength polypropylene, a high melt strengthhigh density polyethylene, an ethylene/propylene copolymer, anethylene/propylene/diene terpolymer, or a combination thereof.
 14. Thepolymer blend of claim 1, wherein the styrenic block copolymer is astyrene-butadiene-styrene block copolymer, astyrene-ethylene-co-(butene)-styrene block copolymer or a combinationthereof.
 15. The polymer blend of claim 1, further comprising at leastan additive.
 16. The polymer blend of claim 14, wherein the additive isa slip agent, anti-blocking agent, plasticizer, oil, antioxidant, UVstabilizer, colorant or pigment, filler, lubricant, antifogging agent,flow aid, coupling agent, cross-linking agent, nucleating agent,surfactant, solvent, flame retardant, antistatic agent or a combinationthereof.
 17. The polymer blend of claim 1, wherein the polyolefin is apolypropylene having a melt strength of at least 6 cN.
 18. The polymerblend of claim 1, wherein the polyolefin is a polypropylene having amelt strength of at least 10 cN.
 19. The polymer blend of claim 1,wherein the styrenic block copolymer is a styrene-butadiene-styreneblock copolymer.
 20. The polymer blend of claim 1, wherein the styrenicblock copolymer is a styrene-ethylene/butylene-styrene block copolymer.21. A polymer blend comprising: (i) at least one ethylene/α-olefininterpolymer, wherein the ethylene/α-olefin interpolymer has: (a) atleast one molecular fraction which elutes between 40° C. and 130° C.when fractionated using TREF, characterized in that the fraction has ablock index of at least 0.5 and up to about 1 and a molecular weightdistribution, Mw/Mn, greater than about 1.3; or (b) an average blockindex greater than zero and up to about 1.0 and a molecular weightdistribution, Mw/Mn, greater than about 1.3; and (ii) at least onepolyolefin, or at least one styrenic block copolymer, or a combinationthereof.
 22. The polymer blend of claim 21, wherein theethylene/α-olefin interpolymer has at least one molecular fraction whichelutes between 40° C. and 130° C. when fractionated using TREF,characterized in that the fraction has a block index of at least 0.5 andup to about 1 and a molecular weight distribution, Mw/Mn, greater thanabout 1.3.
 23. The polymer blend of claim 21, wherein theethylene/α-olefin interpolymer has an average block index greater thanzero and up to about 1.0 and a molecular weight distribution, Mw/Mn,greater than about 1.3.
 24. The polymer blend of claim 21, wherein theα-olefin in the ethylene/α-olefin interpolymer is styrene, propylene,1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, norbornene, 1-decene,1,5-hexadiene, or a combination thereof.
 25. The polymer blend of claim21, wherein the ethylene/α-olefin interpolymer is present in the rangefrom about 5% to about 95% by weight of the total composition.
 26. Thepolymer blend of claim 21, wherein the polyolefin is an olefinhomopolymer, an olefin copolymer, an olefin terpolymer or a combinationthereof.
 27. The polymer blend of claim 21, wherein the polyolefin is ahigh melt strength polypropylene, a high melt strength high densitypolyethylene, an ethylene/propylene copolymer, anethylene/propylene/diene terpolymer, or a combination thereof.
 28. Thepolymer blend of claim 21, wherein the styrenic block copolymer is astyrene-butadiene-styrene block copolymer, astyrene-ethylene-co-(butene)-styrene block copolymer or a combinationthereof.
 29. The polymer blend of claim 21, further comprising at leastan additive.
 30. The polymer blend of claim 29, wherein the additive isa slip agent, anti-blocking agent, plasticizer, oil, antioxidant, UVstabilizer, colorant or pigment, filler, lubricant, antifogging agent,flow aid, coupling agent, cross-linking agent, nucleating agent,surfactant, solvent, flame retardant, antistatic agent or a combinationthereof.
 31. The polymer blend of claim 21, wherein the polyolefin is apolypropylene having a melt strength of at least 6 cN.
 32. The polymerblend of claim 21, wherein the polyolefin is a polypropylene having amelt strength of at least 10 cN.
 33. The polymer blend of claim 21,wherein the styrenic block copolymer is a styrene-butadiene-styreneblock copolymer.
 34. The polymer blend of claim 21, wherein the styrenicblock copolymer is a styrene-ethylene/butylene-styrene block copolymer.35. A flexible molded article comprising the polymer blend of claim 1.36. The flexible molded article of claim 35, wherein the flexible moldedarticle is selected from the group consisting of toys, grips, soft touchhandles, bumper rub strips, floorings, auto floor mats, wheels, casters,furniture and appliance feet, tags, seals, gaskets such as static anddynamic gaskets, automotive doors, bumper fascia, grill components,rocker panels, hoses, linings, office supplies, seals, liners,diaphragms, tubes, lids, stoppers, plunger tips, delivery systems,kitchen wares, shoes, shoe bladders, shoe soles and combinationsthereof.
 37. A flexible molded article comprising the polymer blend ofclaim
 17. 38. The flexible molded article of claim 37, wherein theflexible molded article is selected from the group consisting of toys,grips, soft touch handles, bumper rub strips, floorings, auto floormats, wheels, casters, furniture and appliance feet, tags, seals,gaskets such as static and dynamic gaskets, automotive doors, bumperfascia, grill components, rocker panels, hoses, linings, officesupplies, seals, liners, diaphragms, tubes, lids, stoppers, plungertips, delivery systems, kitchen wares, shoes, shoe bladders, shoe solesand combinations thereof.